ELECTROCHEMICAL STUDIES ON THE

DEVELOPMENT OF NICKEL AND ITS ALLOY PLATING IN

ACETATE BASED BATHS

THESIS SUBMITTED TO ALAGAPPA UNIVERSITY

IN FULFILLMENT OF THE REQUIREMENTS FOR
THE AWARD OF THE DEGREE OF

DOCTOR OF PHILOSOPHY
IN
INDUSTRIAL CHEMISTRY

BY

KR.MARIKKANNU

RESEARCH SUPERVISOR
Dr.G.ParuthJmal Kalaignan

ALAGAPPA UNIVEF(SITr
CENTRAL LIBRa^RY

•* ^ • ^ *to

P1311

DEPARTMENT OF INDUSTRIAL CHEMISTRY

ALAGAPPA UNIVERSITY
(ACCREDITED WITH 'A' GRADE BY NAAC)
KARAIKUDI - 630 003, INDIA

NOVEMBER - 2006
 DECLARATION

I hereby declare that the thesis entitled,

"ELECTROCHEMICAL STUDIES ON THE DEVELOPMENT OF

NICKEL AND ITS ALLOY PLATING IN ACETATE BASED

BATHS" submitted to ALAGAPPA UNIVERSITY, Karaikudi for the

award of the Degree of Doctor of Philosophy in Industrial

Chemistry is my original work and that it has not previously formed

the basis for the award of any Degree, Diploma or any other similar

title of any University or Institution.

(KR. MARIKKANNU)
 CERTIFICATE

This is to certify that the thesis entitled,

"ELECTROCHEMICAL STUDIES ON THE DEVELOPMENT OF

NICKEL AND ITS ALLOY PLATING IN ACETATE BASED

BATHS" submitted by MIss.KR.MARIKKANNU Department of

Industrial Chemistry, Alagappa University, Karaikudi for the award of

the Degree of Doctor of Philosophy is a bonafide record of

research work done by her under my guidance and supervision and

the thesis has not formed the basis for the award to the scholar of

any Degree, Diploma, Associationship, Fellowship or any other

similar title.

Also, certified that the thesis represents an independent work

on the part of the candidate.

Dr.G.PARUTHIMAL KALAIGNAN
( R e s e a r c h Supervisor)

DR. G. PARUTHIMAL KALAIGNAN, M Sc.Ph.D.,

Dr.T.VASUDEVAN READER. ELECTRO CHEMISTRY
(Professor & Head) DEPARTMENT OF INDUSTRIAL CHEMISTRY
ALAGAPPA UNIVERSITY,
Dr. T.VASUDEVAH KARAIKUDI-130 OOV
PROFESSOR AND HEAJ OF THE
OEPARTMENTOF.N0USrK.ALCH.^M,ST^
ALAGAPPA U.^lV-r^SlTY
 ACKNOWLEDGEMENT

First of all I thank The Lord ALMIGHTY for showering upon me His
abundant blessings, strength and wisdom to achieve this task
successfully.

Next I thank my PARENTS and BROTHERS AND SISTER for

providing me their heartfelt supports in all directions.

I would like to express my sincere and heartfelt gratitude to my

mentor Dr.G.Paruthimai Kalaignan, Reader, Department of Industrial
Chemistry, Alagappa University, Karaikudi, as an inspiring personality, for
his keen interest, sound criticism and valuable guidance throughout the
course of this work. Quality lies in his soothing way of communicating the
toughest. I am extremely indebted to him for all his valuable guidance and
generosity.

It is great pleasure to render my sincere thanks and gratitude to

Prof.T. Vasudevan, Head, Department of Industrial Chemistry, Alagappa
University, Karaikudi for his continuous encouragement, kind advice and
valuable guidance throughout this work.

I am immensely thankful to Mr.M.Sankarasubramanian,

Miss.K.SuryaKala, Miss.N.AngayarKanni, DrAR.SathiyaPriya,
Miss.T.Saratha, Dr.S.Sankar and all RESEARCH SCHOLARS for their
helpful suggestions and works.

I take this opportunity to thank my uncle Mr. PK. Sivakumar,and

Mr.S. Malaisamy working in Alagappa university, for their help to join as a
research scholar under Dr.G.Paruthimai Kalaignan.
My grateful thanks are due to the faculty members and non-
teaching members of the Department of Industrial Chemistry and also the
secretarial staff of the University for all their Kindness and help.

(KR.MARIKKANNU)
 CONTENTS

CHAPTER-I
INTRODUCTION PAGE No.

1.1 ELECTRODEPOSITION ... 1

1.1.1 Applications of electrodeposition ... 3
1.2 Metal deposition from simple salt solution ... 3
1.3 Metal deposition from solution of complex salts ... 5
1.4 Electrodeposition of alloys ... 6
1.5 Classification of alloy deposition ... 6
1.6 Factors influencing the alloy deposition ... 7
1.6.1 Effect of plating variables on the composition ... 14
of the alloy
1.7 Characterization of electrodeposits ... 17
1.8 Theory of corrosion ... 21
1.8.1 Classification of corrosion processes ... 21
1.8.2 Electrochemical theory of corrosion ... 21
1.8.3 Heterogeneous theory of corrosion ... 21
1.8.4 Homogeneous theory of corrosion ... 22
1.9 Mechanism of corrosion prevention from coatings ... 23
1.10 Direct current method ... 25
References ... 31

CHAPTER - II

LITERATURE SURVEY AND SCOPE OF THE PRESENT WORK

2.1 NICKEL ELECTRODEPOSITION ... 34

2.1.1 Baths used for nickel electrodeposition ... 34
2.1.1.1 Sulphate bath ... 34
2.1.1.2 Chloride bath ... 35
2.1.1.3 Sulfamate bath ... 35
 2.1.1.4 Pyrophosphate bath ... 36
2.1.1.5 Organic solvents ... 36
2.1.1.6 Acetate bath ... 37
2.1.1.7 Effect of additives ... 38
2.1.2 Application of nickel electrodeposits from
39
various bath
2.2 Ni-Co ALLOY ELECTRODEPOSITION ... 39
. 2.2.1 Electrolytes used for Ni-Co alloy
40
electrodeposition
2.2.1.1 Sulphate electrolytes ... 40
2.2.1.2 Sulphate-Chloride electrolytes ... 41
2.2.1.3 Chloride electrolytes ... 42
2.2.1.4 Sulfamate electrolytes ... 42
2.2.1.5 Acetate electrolytes ... 42
2.2.2. Applications of Ni-Co alloy ... 43
Aim and scope of the present work ... 44
References ... 46

CHAPTER-III
EXPERIMENTAL METHODS
3.1 Materials, Chemicals and Instruments used ... 56
3.2 Bath preparation and purification ... 57
3.3 Hull - Cell measurements ... 59
3.4 Current efficiency measurements ... 60
3.5 Throwing power measurements ... 61
3.6 Cathodic polarization ... 62
3.7 Characterization of Nickel and its Alloy ... 62
Electrodeposits
3.7.1 Physico - chemical characterization ... 62
3.7.2 Weight loss studies ... 66
3.7.3 Potentiodynamic polarization studies ... 67
 3.7.4 Impedance measurements 67
3.7.5 Cyclic Voltammetry 68
3.7.6 UV-visible spectroscopy 68
3.7.7 Scanning electron microscope 71
3.7.8 Atomic force microscope 71
3.7.9 X- ray diffraction 71
References 72

CHAPTER - IV

RESULTS AND DISCUSSION

4.1 STUDIES ON NICKEL DEPOSITION ... 74
4.1.1 Hull cell studies ... 74
4.1.1.1 Effect of bath constituents ... 74
4.1.2 Effect of cunrent density, temperature and
80
pH on the appearance of the deposit
4.1.3 Effect of additives ... 83
4.1.3.1 A comparative account from Hull
88
cell studies on different additives
4.1.3.2 Influence of operating parameters
on the perfomnance of the best 89
additives (Hull cell studies)
4.1.4 Cathode cun-ent efficiency measurements ... 92
4.1.5 Throwing power studies ... 93
4.1.6 Cyclic voltammetry studies ... 95
4.1.6.1 Effect of Sweep Rate ... 95
4.1.6.2 Effect of chloride ions ... 96
4.1.6.3 Effect of nickel ions ... 96
4.1.6.4 Effect of pH ... 97
4.1.6.5 Role of additives in nickel plating
bath ... 97
 4.1.6.6 Effect of Saccharin at different
scan rates Effect of Saccharin at
different scan rates ... 99

4.1.7 Cathodic Polarization Measurements ... 107

4.1.7.1 Cathodic Polarization ... 107
4.1.8 Physical Properties of the Nickel Deposit ... 109
4.1.9 Corrosion resistance characteristics of the
nickel deposits ... 112
4.1.9.1 Weight loss measurements ... 112
4.1.9.2 Potentiodynamic polarization
measurements ... 112
4.1.9.3 Impedance method ... 117
4.1.10 Structural investigation of the nickel
electrodeposits ... 122
4.1.10.1 Surface morphology of the
deposits ... 122
4.1.10.2 AFM studies ... 122
4.1.10.3 XRD studies ... 125
References ... 126
4.2 STUDIES ON ELECTRODEPOSITION OF Ni-Co ALLOY ... 128
4.2.1 Hull cell Studies ... 128
4.2.1.1 Effect of bath constituents ... 128
4.2.1.2 Effect of current density,
temperature and pH on the
appearance of the deposit ... 129
4.2.2 Effect of additives ... 134
4.2.2.1 Cathodic current efficiency and
composition of Ni-Co alloys ... 135
4.2.2.2 Effect of current density ... 136
4.2.2.3 Effect of pH ... 137
4.2.2.4 Effect of temperature ... 138
 4.2.2.5 Effect of addition agent on alloy
composition ... 139
4.2.2.6
Effect of concentration of Co^* in
electrolyte
... 140^
4.2.3 Microhardness of the Ni-Co alloy deposits ... 141
4.2.4 Friction and wear properties ... 142

4.2.5 Cyclic Voltammetry studies for the alloy ... 145

deposits
... 147
4.2.5.1 Effect of sweep rate
4.2.5.2 Effect of pH ... 147
4.2.5.3 Role additives on the
electrochemical behaviour of
Ni-Co alloy on platinum electrode ... 148
4.2.5.4 Effect of sweep rate in the ^49
presence of different additives
4.2.6 UV-Visible spectroscopy ... 159
4.2.7 Corrosion experiments ... 160
4.2.7.1 Potentiodynamic polarization
160
measurements
4.2.7.2 Impedance studies ... 162
... 164
4.2.8 Surface morphology of the deposits
4.2.9 Phase structure Ni-Co alloys ... 164
4.2.10 Cathodic polarization ... 168
4.2.11 Physical properties of the Ni-Co alloy
deposits ... 168
4.2.12 Corrosion behaviour of Ni-Co alloy (47%)
obtained from plating bath containing
additives ... 171
 4.2.12.1 Weight loss studies 171
4.2.12.2 Potentiodynamic polarization .. 172
measurements
4.2.12.3 Impedance measurements . 172
4.2.13 Morphology of the deposits • 177^
4.2.14 AFM studies . 177
4.2.15 XRD studies . 178
References . 185
CHAPTER-V
Conclusions . 187
References . 195
List of publications by the author . 196
 CHAPTER - 1

INTRODUCTION

1.1 ELECTRODEPOSmON

Electrodeposition or electroplating Is the process by which an applied

current or potential is used to deposit a film of metal or alloy by the reduction

of metallic ions onto a conductive substrate. The electrodeposition of

particulates along with a metal or alloy leads to the fomriation of a composite.

Electroplating finds numerous applications as thin films and as three-

dimensional, thick structures in micro devices. The properties of interest for

both thick and thin films cover a broad range, including corrosion resistance,

wear resistance, themnal, magnetic and optical characteristics. Applications

include materials for printed- wiring boards, contacts, connectors and

magnetic recording heads [1, 2].

An electroplating system consists of a plafing bath, a d.c source of

current and two electrodes. The electrode connected to the positive temninal

of the d.c source is anode and negative terminal is called cathode. The plating

baths contain a conducting solution called the electrolyte, which may be

aqueous or non-aqueous or fused salts.

Under the influence of d.c electric current, reactions take place at the

electrodes. The cations move towards the cathode where they are discharged

and deposited as metal.

 M^* +2e ^ • M (lattice)

The anode dissolves to replace the metal ions removed thereby maintaining

the metal ion concentration in the plating bath.

M ^ • M^* + 2e'

The overall process is known as electrolysis. In the case of insoluble anodes

such as stainless steel or platinum, the overall reaction at the anode is the

oxidation of water.

2H2O < • 4H* + 02 +46

Advantages of electrodeposited coatings over the other methods of

coatings are as follows:

1. Avoids the intermediate layer between the coatings and the base metal

as in the case of hot galvanizing and diffusion processes.

2. Generally, electrodeposited coatings have high hardness, good

electrical and themnal conductivity, solderability, reflectivity than

coatings obtained by any other process.

3. The crystal structures of the electrodeposited coatings are very fine

whereas in the case of other processes the crystal structure is coarse.

4. In electrodeposition, the coating thickness can be easily controlled

whereas in the case of galvanizing and other processes the coating

thickness cannot be controlled easily.

5. It is a most reliable method of applying coatings of metals with high

melting points such as copper, nickel, chromium, silver, iron, gold and

platinum than any other methods.

1.1.1 APPLICATIONS OF ELECTRODEPOSITION

The following properties can be improved by electrodeposition:

1. Appearance

2. Corrosion resistance

3. Wear and abrasion resistance

4. Hardness

5. The electric, themnal conductivity, solderability and reflectivity etc.

6. Resistance to high tennperatures

7. Specific magnetic properties

The most important applications of commonly electroplated metals and

their alloy [3] are reported.

1.2 METAL DEPOSITION FROM SIMPLE SALT SOLUTION

Although the technique of electroplating Is well established, the

process can run very smoothly provided adequate control is exercised.

The mechanism of Ion reduction Is extremely complex. A simple outline of

the factors involved is that metal Ions do not exist in the solution in the

simple state (M^^) but have other Ions or molecules associated with them.

Each metal ion usually has a sheath of water molecules around It and it is,

therefore, referred to as a simple hydrated metal Ion. As the water

molecules around do not affect the electrical charge on the metal ion, the

hydrated metal Ion Is represented by M [H20]x^^, where x- is the number of

water molecules in a primary hydration sheath. Figure 1.1 represents a

sequence of phenomenon occurring as indicated below. When deposition

takes, [4] we have

 (a) Transport of hydrated metal ions to the cathode surface.

(b) Partial dehydration of the hydrate, (the removal of water

molecules being confined mainly to the external diffuse layer of

the Helmholtz double layer and occurring in several steps)

(c) Adsorption of the partially hydrated ions at the cathode surface

and diffusion along the surface to low energy positions.

(d) Complete dehydration followed by discharge

M2+ 2e -^ M

(e) Accommodation of the deposited atoms at active sites on the

substrate, leading to the grov\/th of the metal deposits.

Growth point <o

water molecule

o 0

Algnmert of the water ctpoles V)

water Hydrated metal Ion

Helmholz double teyer Diffusion layer Buk of electrolyte

METAL ELECTROLYTt

Fig.1.1 Sequence of events occurring during cathodic deposition

1.3 METAL DEPOSITION FROM SOLUTION OF COMPLEX SALTS

Metals such as copper, zinc, cadmium and silver are commonly deposited

from cyanide baths. In addition to the cyanide baths, plating baths based on

pyrophosphate [5] thiosulphate [6], citrates [7], tartarates [8], acetates [9] are

also used.

In these baths, the ionic species of metal to be deposited are often present

as the negatively charged complex ions. Although, dissociation equilibrium

exists between these complex ions and the simple metal ions, the

concentration of the simple hydrated ions is extremely low because of the

adequate high stability of the complexes. Various possibilities have been

discussed for the discharge of a metal ion M^*^ from its complex as below [10].

a) The deposition of the complex present in the electrolyte into its

components.

For example, [Ag (CN)2r • Ag* + 2CN-

Ag* + e" • Ag

b) The fomnation of a positively charged complex from the existing

negative complex and the discharge of the positive complex as a

whole.

2[Ag (CN)2r • [Ag2(CN)]* + SCN'

[Ag2CNr +e • Ag2CN

Ag2CN • Ag + AgCN

AgCN + CN- • [Ag(CN)2r

Zinc deposition proceeds through Zn (0H)2 as follows:

[Zn (CN)4]^" + 40H- • [Zn(0H)4]^- + 4CN-

[Zn(OH)4f • [Zn(OH)2] +20H-

1.4 ELECTRODEPOSITION OF ALLOYS

With the rapid development of modern science and technology,

there has been a sharp Increase In the electrodeposltlon of more than one

metal or a metal with a ceramic material. Electroplated alloy coatings

satisfied most of the requirements like appearance, protective properties

against deterioration, to achieve decided hardness, phase structure and

sometimes amorphous coatings.

1.5 Classification of alloy deposition

Alloy deposition may be classified as follows: (i) Regular (ii) Inregular

(iii) Equilibrium (Iv) Induced and (v) Anomalous [11].

Regular co-deposition

It is characterized by the deposition being under diffusion control. The

effects of plating variables on the composition of metal Ions In the cathode

diffusion layer are predictable from simple diffusion theory. Regular co-

deposition is most likely to occur in baths containing simple metal ions, but

may occur in baths with the static potentials of the metals are far apart and

with metals that do not fomri solid solutions.

Irregular co-deposition

It is characterized by being controlled by the Idiosyncracies of the

potentials of the metals against the solution to a greater extent by diffusion

phenomena. The effects of plating variables on the composition of the deposit

are much smaller than with the regular alloy plating systems. Irregular co-

deposition Is most likely to occur with the static potentials t)fth&parentfnetals

are markedly affected by the concentration of the complexing agent. Brass

deposition, for example, is a process of irregular co-deposition.

Equilibrium co-deposition

Equilibrium co-deposition is characterized by deposition of an alloy

from a solution, which is in chemical equilibrium with the constituent metals.

Copper - Bismuth, and Lead - Tin systems fall into this category, the ratio of

the metals in the deposits being the same as that in the bath.

Anomalous co-deposition

It is characterized by the anomaly that the less noble metal deposits

preferentially. It is frequently associated with the electrodeposition of alloy

containing one or more of the 3 metals of the iron group, i.e. Fe, Co and Ni.

Induced co-deposition

It is characterized by the deposition of alloys containing metals such as

Mo, W or Cr, which cannot be deposited alone. However, these readily co-

deposit with the iron group metals. The effect of the plating variables is

unpredictable.

1.6 FACTORS INFLUENCING ALLOY DEPOSITION

From the EMF series, it is known that the standard potentials of zinc

and copper vary widely, that is, 1.1 V and it is much easier to deposit copper

than zinc. It is very difficult to deposit both the metals simultaneously from

simple salt solutions (sulphate solutions). To co-deposit these two metals, it is

essential to bring their potentials together by complexation. Complexation of

ions of a metal gives rise to a very low free-metal ion concentration and hence

copper potential is brought nearer to that of zinc.

Concentration of metal ions in the solution

Copper has the equilibrium potential of + 0.52V (for Cu") and + 0.34V

(Cu^*) and zinc has the potential of -0.76V. By complexing cuprous ions with

cyanide, a very large change in concentration is brought about with a

corresponding change in potentials.

The equilibrium constant for reaction

[Cu(CN)3f- ^ • Cu* + 3 C N -

The equilibrium constant was found to be 5.6 x 10"*', when [Cu (CN)3]^"

concentration is 5 x 1 0 ' * M and cyanide concentration 2.65 x 10"* M. The

concentration of monovalent copper was calculated to be 1.5 x 1 0 \ Using

Nernst equation, Ecu becomes (0.52 + 0.059) log (6.62 X 10"''®)

= -0.54 V and for 2.5 X 10 "^ M [Zn (CN)4] ^'

E zn = -0.76 + 0.059 log (6.62 X 10 -^)

= -0.85 V

Thus by complexing, the potentials of copper and zinc can be brought

together.

There is always a different in the discharge of metal ions at the

cathode, which causes their continuous depletion in diffusion layer. The

depletion of ions is made good by diffusion from the bulk of the solution and

the supply is improved by agitation of the electrolyte, heating or stirring of the

cathode. For specific rate of agitation or stirring, use of higher current density

brings about an increase in the deposition rate upto a certain level, i.e. upto

the limiting current density.

Hydrogen overvoltage

Generally all alloy plating systems except lead and tin are associated

with substantial hydrogen evolution. Evolution of hydrogen influences the

deposition mechanism and the mechanical properties of the depQ^

also have a secondary inhibiting effect on the deposition mechani!

Polarization behaviour of alloy systems \;^-//S^'5> v

Let us consider qualitatively the factors, which influence the

composition of binary alloys. Figure (1.2) represents the polarization curves

for the deposition of two metals Mi and M2 from the same electrolyte. The

potentials of A and C correspond to zero metal deposition rate and diverging

from these reversible potential each curve shows the initial characteristic

linear section. Let it be assumed that no other cathodic reactions take place

(such as H2 evolution) during alloy deposition. At the cathode potential ei, ii

and i2 are the c.ds giving the rates of discharge of two types of metal ions.

Since both metals depositing on the same area of cathode, the c.ds, ii and k

are in the same proportion of the corresponding curves, ii and h the weights

of the two metals co-deposited given by (ii wi t /F) and (ia W21 /F) where 't' is

the time of deposition in seconds and wi and W2 are the equivalent weights of

metals; the weight ratio of one metal to the other in the alloy is (ii wi / i2 W2)

and it is evident from Figure (1.2) that the composition of the alloy is

dependent on the relative positions and slopes of the polarization curves for

the two separate metal deposition processes. If the two polarization curves

are different in position only so that they would actually superimpose if they

had one point in common, then the composition of the alloy given by the ratio

(ii /12) would be independent of the total rate of deposition of the alloy, this
rate being (ii + i2 )• On the other hand, if the polarization curves are different

in the initial slope, than the composition of the deposited alloy is independent

of its rate of deposition.

Figure (1.3) illustrates how the deposition potentials are more negative

than E° values but the degree of polarization varies from metal to metal. At a

point of intersection or convergence, a potential exists at which both metals

may electrodeposit and co-deposition results. The two polarization curves

cross at a point X.

^e C

[Vl A

e \
1
^
1
_jr^>->!^
^"^ D

V B

v
e
i, ii
i CinAcm-2)

Fig. 1.2 Conditions of polarization of two metals (IMi & l\/l2)

having similar E-i curves

10
 (mA-cnT^)

Fig. 1.3 Conditions of polarization co-deposition of two metals

(Ma polarization is more than Mi)

At this point (Ex) the current densities (ix) proportional to the deposition

ratios of either metal, are equal and the weight composition of the alloy is

given by (W1/W2). At cathode potentials less negative than Ex (say at

Ey), the rate of deposition of the alloy is less than at potential Ex and its

composition is equal to ( iiy Wi - i2y W2 ). The opposite is the case at

cathode potentials, more negative than Ex (say at Ez). Here the alloy is

depositing faster than E x and it is richer in metal M2.

If hydrogen is evolved during the plating of an alloy, the probable

effects of variables such as pH and temperature on the composition of the

alloy can be assessed from the knowledge of relative slopes and positions of

polarization curves (including that of H2). If the current yield of deposition of

the alloy is low owing to considerable H2 evolution, the potential of the

cathode may be almost by the H2 evolution reaction. A situation may arise

when on account of the generally greater inreverslbHity of the H2 reaction, the

11
currents corresponding to the deposition of each metal of the alloy are close

to the limiting values Figure (1.4). Under these conditions, it is evident from

the figure that most of any increase in cell current is accounted for by

increased H2 evolution but that composition of the alloy at the same time, is.

changed only to a minor extent.

i (mA.cm"2)

Fig. 1.4 Polarization curves for alioy deposition with

simultaneous evolution of hydrogen

Growth Mechanism

The kinetics of alloy plating depends on the differences in the crystal

growth mechanism goveming the structural characteristics, such as, the

crystal size, shape, presence of texture and its type, the defect structure of

the lattice etc. The phase composition is an important factor, which depends

on the conditions of cathodic reduction and affects the kinetics of the

reduction of the alloy components.

12
Addition Agents [12-15]

The effects of addition agents on co-deposition may be exhibited by the

fomriation of dense adsorption films on the cathode or they may have specific

effects on their crystals growth. They may remain incorporated within the bulk

of the growing crystal lattice and have great influence on the structure of

deposits. In most cases, their incorporation in the deposit is associated with

an increase in the overpotential or at times depolarization, thus causing a

change in the phase structure.

Phase Structure

The rate of deposition is greatly influenced by the phase structure of

the alloy. The polarization curves of the overall alloy deposition process have

a section corresponding to a sharp increase in the cathode potential at a

constant current density. In the polarization curve, the constancy of current

over a range of potential has been interpreted as difficulties in the formation of

a new phase.

Actually a new phase is formed when the solubility limit of the

electronegative component in the primary phase is reached [16]. This limit

depends on purely structural factors, such as, the size ratio of the atoms of

the alloy components, electronic configuration etc. This may often affects the

kinetics of the overall process. At the same time, the new phase may have an

influence on the ion discharge kinetics on its surface In accordance with the

position of the zero charge potential of its surface and with the sign and

magnitude of the charge of the electrical double layer.

13
1.6.1 EFFECT OF PLATING VARIABLES ON THE COMPOSITION OF THE

ALLOY

The composition of electrodeposited alloy is a function of large number

of variables.

Variables of bath Composition

a. The variation of the total metal content of the electrolyte produces

relatively small effects on the composition of the alloy compared to

that of the ratio of the concentrations of various metal ions in the

electrolyte.

b. An increase in the concentration of the complexing agents [17-19]

in the electrolyte, affects the composition of the alloy, by suitably

modifying the activity of the metal ions. In case of solutions having

mixed type of complexants, the composition of the alloy can be

easily altered in the same manner.

c. The presence of addition agents, at times, preferentially inhibit the

deposition of one of constituent metals of the alloy and change its

composition and phase structure.

d. Different salts added to increase the conductivity, change the

polarization characteristics and hence the composition of the alloy.

Variables of Operating Conditions

a. An increase in current density results in higher polarization and

therefore favours the metal depositing at a more negative potential

or the one depositing less readily.

14
 b. The composition and stability of many complex ions are affected by

variation in solution pH [20-24]. As the pH of the electrolyte

increases, the relative ease of complexation of the two metals can

differ appreciably leading to significant change in the alloy

composition. Generally, increase in pH of the electrolyte favours

the co-deposition of the metal depositing at a more negative

potential.

c. Increase in electrolyte temperature affects (1) equilibrium potential

(2) polarization effects (3) concentration of metal ions at the

cathode diffusion layer (4) current efficiency, etc. In general, an

increase in temperature of the electrolyte favours the deposition of

the more noble metal.

d. By stirring the electrolyte, the metal ion concentration in the

cathode solution interface increases and hence the deposition of

the preferentially depositing metal is favoured. However, in

solutions containing complexing agents, due to the reduced free

compiexant concentration, at the cathode-solution interface, during

stirring, the above effect may vary.

Other Variables

a. The cathode current efficiency with which each constituent metal

gets deposited during co-deposition detemnines the composition of

the alloy.

b. The overpotential required to initiate the deposition of each metal

varies with the substrate material [25, 26]. The deposition of one

15
 metal may be more favoured than the other due to the above

reason and hence, the composition of the alloy can differ from

substrate to substrate. The roughness and structure of the

substrate also affect the appearance, adhesion, porosity, cathode

efTiciency, composition and crystal structure of alloy deposits.

c. The anode [27] selected should have a composition similar to that

of the depositing alloy and also corrode unifomnly to avoid

chemical imbalances in the electrolyte. The use of soluble anodes

for alloy plating is associated with the difTiculty of displacement

reactions since neither the constituent metal nor the alloy is in

chemical equilibrium with the bath. In the case of insoluble

anodes, the concentration of depositable metal ions in solution

drastically decreases and at times they may even get oxidized.

The pH of the solution gets altered and it is very difficult to achieve

unifomn alloy composition unless rigorous precautions are taken to

replenish the bath with metal ions.

d. The unifomnity in alloy composition, the physical and stmctural

properties of the deposits vary with the type of current source

used, viz. (1) Direct current (2) direct current superimposed with

alternating current (3) pulsed current (4) periodic reverse current

(5) periodically reversed pulsed current. Plating in ultrasonic or

magnetic fields also helps in producing better quality deposits.

16
1.7 CHARACTERIZATION OF ELECTRODEPOSITS

a) Adhesion

The adhesion of an electrodeposit is an important measure of its

serviceability but satisfactory tests are difficult to devise. According -to

Hothersall [28] adhesion can be defined as the force required for separation of

the deposit from the base metal. The principal causes for poor adhesion are:

I. The presence of a foreign material between the coating and the

base metal

II. The presence of a weak layer of metal either upon the surface plated

or on the initial deposit, and

III. The incidence of stress in the deposited metal.

Adhesion testing methods [29, 30] can be broadly classified into (i)

quantitative test and (ii) qualitative test.

The quantitative tests such as Ollard test, Cobalt nodule test and Peel

test require a thick deposit, which is time consuming to produce. Hence, it is

not suitable for testing the thin coatings actually used in service conditions.

The qualitative tests are simple and have some significance for the

practical plater, but are of little value for precise specifications. Operations

which can be included in this category are filing, cupping and themnal cycling.

In the bend test method [31] the specimen was bent back and forth through

an angle of 180° until fracture of the basis metal occurs and the defects were

observed under low magnification optical microscope for separation or peeling

or flaking off the coating, if any.

17
b) Hardness [32]

The hardness of the surface is measured by the resistance offered to

penetration when a hardened steel or diannond tipped penetrator of precise

geometry is impressed on to the surface under a known load. By measuring

the size of the indentation and by using a fomnuia correlating the indentation

size with the test load, it is possible to calculate a hardness number. The

hardness measurement of a coating involves the selection of a suitable shape

of the indentor and the method of applying the load. There are two methods

namely Vickers and Knoop methods.

The main difference between these two methods is the shape used in

the indentation. In the Vickers method, the indentor is a symmetrical pyramid

with an included angle between the faces of 136°. The measurement is made

by taking the average of the two diagonals. The Knoop indentor Is a non-

symmetrical pyramid with included angles between corners of 130° and

172.5°. Only the long diagonal is measured.

The hardness can be calculated by using these formulas

1.854x1
Hv=

HK =
0.070^

Where Hv and Hk are the Vickers and Knoop hardness numbers, L is the load

kg and D is the diagonal of the indentation I mm, this means that the Vickers

and Knoop hardness numbers have units of Kg/mm^.

18
c) Porosity

Porosity of electrodeposited coatings can be defined as the degree of

uncovered microscopic regions of the base metal [2, 33]. In general, the

degree of porosity of a deposit decreases with increasing thickness. Porosity

is however important in the case of deposits which are nobler than the base

metal. Since in such coatings the rate of corrosion at the pores is likely to be

accelerated.

A traditional and reliable chemical test for porosity is based on the

application of a suitable reagent which will react with the base metal through

pores in the coating but will not attack the deposit. Usually the reagent causes

a distinctive colour spot at each pore. Ferroxyl test [34] was employed for the

coatings obtained on the mild steel substrates. The evolution of porosity was

made on the basis of the number of blue spots fomned by the chemical

reaction between the reagent (potassium ferricyanide) and the exposed steel

substrate

K3 [Fe (CN)6] + Fe^* • K FeIFe(CN)6]+ 2K*

"Prussian blue"

d) Stress

Electrodeposited metal coatings often have internal stresses which

strongly affect the mechanical properties of the electrodeposits. Thus, tensile

stress can lead to cracking and peeling of the coating and also considerably

decreases the fatique strength of parts. The codeposited hydrogen

incorporated into the deposit is responsible for the internal stress by causing a

temporary lattice expansion in the deposited metal [35].

19
e) Ductility [32]

Ductility is one of the physical properties of a metal. The ability of a

metal to deform plastically without fracturing. The more ductile a deposit is,

the less likely the metal will crack in service.

f) Solderability [32]

The solderability of a deposit refers to the ease and uniformity of

wetting the deposit by solder used In the solderability tests of 60-63% Sn and

40-37% Pb. Tin is the active constituent promoting wetting and lead is an

inactive dilutent.

g) Electrical resistance [32]

The electrical resistances of electrolytic metal coatings play an

important role. The specific resistance of electrodeposited pure metals

approximates that of cast metals. The specific resistance of electrodeposited

metals can be intermediate between that of the cold-worked and the

recrystallized metal.

Even small quantities of impurities can cause a considerable increase

in the specific resistance. Thus, the specific resistance of electrolytic silver

containing only 0.02% glycol is 1.9x10'*Qcm for a pure silver deposit obtained

from a cyanide bath.

h) Wear resistance [32]

Electrodeposited coatings are often subjected to sliding and friction

wear. The main purpose of hard chromium plating is generally to protect

against wear and increase the service life of the devices and machine tools.

20
Hardness and wear resistance often go hand to hand, the surface becoming

more wear-resistant with Increasing hardness of the deposit.

1.8 THEORY OF CORROSION

1.8.1 Classification of corrosion processes

Corrosion of metals may be defined as spontaneous processes of

destruction in the course of their chemical, electrochemical or biochemical

interaction with the environment. Electrochemical corrosion is encountered

more frequently than other types of corrosion and is the most dangerous to

metals. It may also occur in a gaseous atmosphere when moisture condenses

on the metal surface.

1.8.2 Electrochemical Theory of Corrosion

A significant amount of electric current was first generated by the

phenomenon of corrosion in the well known voltaic pipe. Faraday [36] in 1834

established the close relationship between current and chemical reactions.

Faraday put fon^/ard the nomenclature of electrolytic cells and the two basic

laws governing the relationship quantitatively.

1.8.3 Heterogeneous Theory of Corrosion

Evans and Hoar [37] demonstrated that a cell was set up between the

upper and lower portions of a steel specimen when immersed in potassium

chloride solution. They measured the current flowing between the upper and

lower portions by cutting the specimen and joining the cut edges together with

a wax coating. They also plotted the potential against the current for the two

regions and got a polarization diagram (Fig 1.5) called Evans diagram. The

current corresponding to the intersecting point in this diagram is correlated

21
with the weight of metal dissolved in accordance with Faraday's Laws. This is

also known as local cell theory of corrosion and is illustrated by Ferroxyl

indicator test [38].

The anodic reaction taking place at the anodic sites is the metal

dissolution reaction as represented by

M • M"* + ne

M stands for the metal, n for the number of electrons and e" for the electrons

released at the anodic sites, which travel to the cathodic site and have to be

used up there. The consumption of electrons released during the dissolution

reaction can take place in two ways. In acidic media, the H^ ions will combine

with them and hydrogen gas will be liberated at the cathodic sites as below.

nH"" + ne" nH

2nH ^ nH2T

O2 +2H2O + 4e- • 40H-

In local theory of corrosion according to original assumption, cathodic

and anodic process is spatially separated and each of these reactions

proceed only on this basis, that ideally pure metals with a highly

homogeneous surface area or not subject to corrosion.

1.8.4 Homogeneous theory of corrosion

It is not necessary that cathodic and anodic reactions should take place

at spatially separated areas. Often two or more electrode processes may take

place independently of each other on the same metal surface. For example

iron dissolves in acid solutions giving ferrous ions. Simultaneously, hydrogen

ions are discharged and give rise to hydrogen

22
 (Amp) corr

Fig. 1.5 Evan's Diagram

gas. These reactions can take place on the same metal surface at the

observed electrode potential. This concept of mixed potential was first put

forward by Wagner and Traud [39] and later by Frumkin [40].

1.9 MECHANISM OF CORROSION PREVENTION BY COATINGS

Electrodeposition of iron and steel with nickel for protection against

corrosion has been known since 1840. The coating applied sen/es as a

barrier between the steel and the environment. Metallic coatings can be

divided into two categories, namely:

1. noble metal cathodic coatings, and

2. anodic or sacrificial coatings

Coatings such as nickel, tin, zinc and chromium etc. are used to keep

out air and moisture from the surface of iron or steel. Such a coating is

cathodic to steel and is of pitting due to the formation of dangerous corrosion

23
cells with combination of small anodic sites with large cathodic ones. At

exposed pores, the galvanic current eventually undermines the coating. This

effect is appreciably reduced by the stifling action of corrosion products. It

may be assumed that under specific conditions, discontinuous cathodic

coatings can also electrochemically produce the coated metal by anodic

polarization of bare areas, thereby maintaining the passive state and hence

stifling of corrosion. Pores in the noble metal coating lead to penetration

attack at the bottom of pores which are anodic.

Zinc, cadmium and aluminium are sacrificial coatings for steel. If the

cathodic reaction for corrosion is one of hydrogen evolution, depending on the

hydrogen overpotential corrosion rates become different. If coupled to

platinum, iron is more corroded, while with zinc, the corrosion is retarded.

The protective property of zinc on iron is also limited by the blockage of

corrosion cells. When zinc is involved, iron combines with hydroxyl ions

produced by the cathodic reaction on the steel surface and precipitates as the

hydroxide within the minute gaps of the coating. If the base metal is coupled

with another metal, mechanism of corrosion is changed. Coatings of zinc and

cadmium soon after their production are passivated by chromate conversion

coatings. A thin chromate film retards corrosion by acting as a barrier layer

[41]. Chromating of zinc is usually carried out into the pH range 1.2-1.6 and

basically involves:

a) Zinc dissolution

b) Precipitation of chromium hydroxide and chromate ion

formation and

c) Fomnation of basic chromium chromate film.

24
 Chromate coatings have a tendency for self healing since the

chromates are quite often insoluble, diffusion fronn the surrounding areas

leads to passivation of the exposed surface. They provide an excellent base

for paints with good adhesion.

1.10 DIRECT CURRENT METHOD

1. Logarithnnic polarization Method

The E-iog I relationship is obtained either by galvanostatic or by the

Potentiostatic method. The galvanostatic method involves the use of a

constant current generator, a three electrode cell assembly and a high

impedance voltmeter. The current is passed between the test and auxiliary

electrode. The resulting electrode potential is measured against a reference

electrode. While the anodic current represents the rate of net oxidation, the

cathodic current represents the net reduction process, in the Potentiostatic

method, the Potentiostatic maintains a constant potential and the current flow

between the test and auxiliary electrode is followed. The anodic and cathodic

polarization curves are plotted and the linear regions (Tafel lines) are

Identified in E-log I plots on either side of corrosion potential. Extrapolation of

linear segment regions to Ecorr, (intersection of Tafel lines) gives the constant

current. The measurements are to be made over at least three decades of

cunrent density. The corresponding surface, however, changes with time.

2. Linear Polarization (Polarization Resistance) Method

The method employs polarization within 20 mV of the corrosion

potential, as the relationship between overpotential and current is linear in this

range. The corrosion currents are obtained using Stern Geary equation [42].

25
 baXbc
/a A uc 6r\
' corr ~
2.303 (ba + be) L di J

This method is quick, requiring not more than thirty minutes. Because

of the small perturbation, the system is not affected significantly. This method

requires knowledge of ba and be and the values of corrosion current depend

on the way in which ba and be are obtained. The TI-I plots around the corrosion

potential will be distored in the case of diffusion controlled processes

depending upon the time at which measurements are made, i.e, '11' with

reference to T or vice versa. The ohmic drop contributions will lead to

erroneous measurement of icorr-

3. Relaxation Method

So far, the discussion has been confined only to steady state

techniques. In the steady state, all the charge transfer processes and the

concentration of the species should be constant with time. In other words, the

concentration gradient between the electrode/electrolyte interfaces should be

invariant. Such a situation is possible only in the case of a small interval of

time. One can vary either the potential or current stepwise or in a periodic

manner and follow the changes of current or potential with time. These

variations are governed by mass transport. In non-steady state methods, the

non-Faradaic current is always associated with Faradaic current. The non-

Faradalp currentjs used for chafg^the double layer. The total current is the

sum of that used for initially charging the doublaiayfiE and that for the.

electrode process to occuc.

26
 'total - if + inf

The relaxation techniques help to detennine the polarization resistance

free of ohmic drop and nnass transport effects.

Rp = Rt+RiR+Rc

Where Rp is the total polarization resistance and Rt the charge transfer

resistance which Is proportional to (icorr)-

The relaxation techniques used commonly in corrosion studies are the

charging curve method, the potential and current step methods and the

coulostatic method. The charging curve method requires the measurement of

both Tafel slopes by some other means. The step methods enable one to

detemnine the charge transfer resistance eliminating mass transfer and hence

give instantaneous corrosion rates. The coulostatic method offers a unique

method of finding Tafel slopes, charge transfer resistance and hence the

corrosion current. It is applicable to highly non-conducting media.

4. Faradaic Impedance Method

The corresponding metal and the metal solution interface can be

viewed as combinations of passive circuit elements involving capacitance,

resistance and inductance. In d.c methods (a special case of a.c where the

frequency equals OHZ the resistance obeys the ohm's law E=I.R. For a.c,

where the frequency is non-zero, the anomalous equation E = I.Z holds good.

In this equation, E and I are wave fomn amplitudes for potential and current

respectively and Z is the impedance, the a.c. equivalent of resistance. The

application of altering voltage results in alternating current. The sine wave

current thus produced can be described by the equation.

27
 I = A' sin (ot + O)

Where

I = instantaneous current

CO = Frequency of radians

A' = Maximum amplitude and

O = Phase shift in radians

Any a.c. current vector can be defined as the sum of its real and

imaginary components.

itotai = r + r j : j = (-i)'''
Similarly any a.c. voltage vector can be expressed as

Etotal = E- + E" j

The real and imaginary components of an a.c. waveform are defined

with respect to some reference wavefomn. The real component is in phase

with the reference waveform and the imaginary component, also referred to

as the "quadrature component" is exactly 90° out of phase. The reference

wavefomi allows expression of the current and voltage waveforms as vectors

with respect to the same co-ordinate's axes and this facilitates mathematical

manipulation of the Vector quantities.

Specially, this allows one to calculate the impedance vector as the

quotient of the voltage and current vector.

E' + E" i

I' + I" j

The resulting expression for the a.c. impedance as given by the equation.

Ztotai = Z' + Z" i

28
And is defined in temis of the same co-ordinate axes, the current and voltage

vectors.

The absolute magnitude of the impedance can thus be expressed as

Z = V(zf + {Z'f
As the components of the circuit elements contain a frequency term,

the impedance representing these circuit elements will vary with frequency.

When the imaginary component of the impedance Z" is plotted against

the real component Z' at each execution frequency, one would obtain Nyquist

or Cole-Cole plot. Fig. 1.6 gives the a.c. impedance profile for a simple

electrochemical system.

At high frequencies only the uncompensated resistance contributes to

the real portion of impedance, while at very low frequencies the polarization

resistance also contributes to the measurement. Once the excitation

wavefomi becomes much faster than the charge transfer rate. The

electrochemical impedance (Rp) becomes transparent to the technique. An

Ohmic resistance (Rs) on the other hand, will represent constant impedance

at all frequencies. This is consistent with the fact that Rp can also be

measured by the d.c technique while Rs cannot. The polarization resistance

can be used for calculation of the corrosion rate of an electrode material.

29
 Rs + Rp

Fig 1.6 a.c. impedance profile for a simple

electrochemical system

30
References

1. E. Gomes, E.Valles, J. Appl. Electrochem.29 (1999) 805.

2. B. Lochel, A. Maciossek, J. Electrochem. Soc. 143 (1966) 3343.

3. H.Silmen, G.lsserlis and A.F. Averill, 'Preventive and decorative coatings"

for metals', Finishing Publications Ltd., England, 1978.

4. H. Gerischer, Zur. Kinetik der. Ag/Ag (aq). Electrode Processes, 9'^

Meeting. International. Comm. Electrochem. Thermodyn. Kin (K.I.T. C.

E) Pairs (1957) p. 352.

5. T.L Ramachar, Electroplat. Metal. Finish, 10 (1957) 347, 391,408.

6. RM. Krishnan, S. Sriveeraraghavan and S.R. Natarajan Bull.

Electrochem . 2 (3) 1985 p.257.

7. RM. Krishnan, S. Sriveeraraghavan and S.R. Natarajan First

International Conference on Electrofomning and Electrodeposition,

Bangalore; 1986.

8. A.K. Graham and H.J. Read, Metal. Ind (N.Y)

35,1937,559,617

36, 1938, 15, 17,120,169.

9. S.M ABD EL WAHAA, A.M ABD EL-HALM, S.S. ABD EL REHIM and

E.A. ABD El MEGUID. Surf. Coat. Technol, 29 (1986) 313.

10. RM. Krishnan, S.R. Natarajan, V.S. Muralidharan and Gurdeep Singh

10* International Conference on Metallic Corrosion Reprints, Nov. 1987,

p.1325.

11. Abner Brenner, Electrodeposition of Alloy, Vol.1, Academic Press, N.Y.

(1963), p.413.

31
12. T.C. Franklin, Electrochem. Soc, 168th Fall Meeting, Extd. Abst, 85-2,

229,347,(1985).

13. T.C. Franklin, Surf. Coat. Technol, 30 (1987) 415.

14. K.I. Popov, Z.P Rodaljevic, N.V. Krstajlc and S.D. Nonakovic, Surf.

Technol, 25, (1985)217.

15. B.N. Afana'ev, Electrokhimica, 28, (1984) 1056.

16. N.F. Khomutov, Electrodeposition of metals and Alloys. Israel

Programme for Scientific Translation, Jerusalem (1986).

17. E.J Derhun & T.Z. Fahidy, J. Electroanal. Chem, 16, (1986)

82.

18. M. Fleishman, H.R. Thirsk, Advances in Electrochemistry and

Electrochem. Eng, Ed. P. Delahey and C. Tobias, 3, (1963) 124.

19. A.N. Frumkin, Electrokhimica, 1, (1965) 394.

20. L.T. Romankiw, Electrochem. Soc, 170*" Fall Meeting, Extd. Abst,

86-2,(1986)682.

21. K.E. Heusler, Electrochim. Acta, 30, 12, (1985) 1741.

22. J.O'M. Bockris and A. Damjanovic, Modern Aspects of Electrochemistry,

Vol.3, Butterworths, London, p.224, (1964).

23. J. Matulis and R. Slizus, Electrochim. Acta, 9, (1964) 1177.

24. L.B. Harris, J. Electrochem. Soc, 120, (1973) 1034.

25. G. Peslerbe and B. Nguyen, Surf. & Coat. Technol, 28 (1986) 57.

26. Chr. Bozhkov and St. Rashkov, Proc. 37*" Internatl. Soc. for

Electrochem, 1, 02-18 (1986) 49.

27. D.A. Swalheim, Plating & Surf. Finish, 72, (1985) 16.

28. A.W. Hothersall, J. Electrodeposit. Soc, 13, (1937) 12.

32
29. D. Davies and J.A. Whittaker, Metals and Materials, 1, (1967) 2.

30. H. Plog, Galvanotechnik, 61,(1970) 155.

31. ASTM Teat Method B571-84, Adhesion of metallic coatings, American

Society for Testing and Materials, 1985.

32. A.C. Tan (Ed), Tin and solder plating in the semiconductor Industry,

Chapman & Hall, London, 1993.

33. J.K. Dennis and T.E. Such (Ed) Nickel and Chromium plating,

Buttenworths, London, 1986.

34. ASTM Teat Method 8689-81, Electroplated engineering nickel

coatings, American Society for Testing and Materials, 1986.

35. E. Raub and K.Muller (Ed) 'Fundamentals of Metal deposition',

Elsevier Publishing Company, New York, 1967.

36. Faraday' Dairy, 1-7, G. Bell and Sons, London (1932-1936).

37. U.R. Evans and T.P. Hoar, Proc. Roy. Soc, A.I37 (1932) 343.

38. U.R. Evans (Ed) 'An Introduction to Metallic Corrosion", Edward Arnold,

London (1963) p.31.

39. Wagner and Traud, Z. Phys. Chem., 182 (1938) 441.

40. A.N. Frumkin (Ed) 'Kinetics of Electrode Processes' Moscow

University Press, Moscow (1952).

41. R.L. Saur (Ed) Properties of Electrodeposits, Their Measurement and

Significance, The Electrochem. Soc. Inc., New Jersey, 1975, p.70

42. M. Stern and A.L. Geary, J. Electrochem. Soc, 104 (1957) 56.

33
 CHAPTER -II

LITERATURE SURVEY AND SCOPE OF THE PRESENT WORK

2.1 Nickel Electrodeposition

Nickel and chromium are two metals widely electroplated for decorative

and functional purposes. Nickel is an accepted corrosion resistant coating

metal. Nickel electroplating is one of the most important industrial processes

that find a wide range of applications utilizing the desirable decorative,

protective, magnetic and mechanical properties of nickel [1]. The appearance

of a magnetic dependent electrical resistivity for films with rougher interfaces

is of technical interest for applications as magnetic reading heads [2].

2.1.1 Baths used for nickel electrodeposition

2.1.1.1 Sulfate bath

The electrodeposition of nickel was first described in 1837. G. Bird

electrolyzed solutions of nickel sulphate or nickel chloride for some hours and

so obtained crust of metallic nickel on a R electrode. Nickel is mainly

electrodeposited from nickel sulphate solutions which contain a certain

minimum of chlorides. It was proposed by Watt's in 1916 [3]. The effect of

plating variables on the structure [4] and properties of electrodeposited nickel

has been studied [5].

A special attention has been paid to the throwing power as well as

visual appearance, current efficiency and co-deposition of foreign atoms and

throwing power index was reported [6,7]. The amount of sulfur incorporated

into nickel plated from a Watt's bath containing thiourea as a brightener and

leveler has been investigated by radiotracer techniques [8]. Porosity was

34
determined for nickel coating from Watt's batli through anodic voltammetry

[9]. Effects of oxalate in Watt's bath have been studied by A.J.Steiger et .al.

[10]. The themnal instability, magnetic property of nickel films was reported

111.12].

Wastson [13] reported that addition of chromium particles to a Watt's

bath shifted the nickel electro reduction wave to more positive potentials on

various carbon electrodes. Gogia [14] studied the polarization behaviour of

nickel in the presence of cationic impurities such as Co^* , Cu^"", Fe^"", Fe^"^

and A P * , Cr^l15], Cd^* [16]. Basic aspects of nickel plating and the

troubleshooting of bath has been reported [17, 18]. Electroforming of nickel

from Watt's bath was reported [19].

2.1.1.2 Chloride Bath

The electrodeposition of nickel has been studied by various workers in

terms of polarization measurements [20-27], structural studies [28-32] and

efficiency measurements [26-33]. The cathodic polarization and current

efficiency with respect to nickel deposition have been measured in chloride

solution as a function of nickel ion concentration, pH and temperature [34, 35].

Resier and Fischer have reported the simultaneous deposition of hydrogen

and nickel from a nickel chloride-hydrochloric acid solution [26].

2.1.1.3 Sulfamate bath

The nickel Sulfamate bath, first used commercially in the U.S.A. about

1950. Nickel Sulfamate bath containing boric acid are widely used for the high

speed electroplating of nickel because it is easier to obtain thick deposits with

less internal tensile stress from this bath than from Watt's-type baths [36-38].

35
A detailed investigation was done by Fanner and Bush et.al with the effect of

process variables on the physical properties of deposits obtained from nickel

sulfamate bath [39, 40]. A comparative study was described with the

sulfamate and Watt's bath on the basis of stress measurements [41]. The

nickel sulfamate -chloride baths was reported by DIggin et.al [42]. Influenqe of

Sonication in a nickel sulfamate bath was investigated [43].

2.1.1.4 Pyrophosphate bath

The pyrophosphate bath has been found to be satisfactory for the

plating of nickel. It gives good quality deposits over a wide range of operating

conditions and has some advantages over the Watt's bath. Fluoborate and

sulfamate types have a poor throwing power and are not suitable for direct

plating on zinc. Langbein [44] cites an alkaline nickel pyrophosphate and

there is a patent [45, 46] containing nickel in the fomn of ammohlcal

pyrophosphate. Basic aspects of pyrophosphate bath were reported [47, 48]

and a general review of plating metals and alloys from the pyrophosphate

bath was described [49, 50]. S.K. Panikkar et.al reported on the cathodic

polarization and surface morphology of the deposits [51].

2.1.1.5. Organic solvents

Electrodeposition of nickel from non-aqueous solvents and the effect of

bath constituents and effect of additives were reported [52]. The

electrochemical behaviour of nickel has been studied in different types of

aqueous and organic solvents [53].

36
2.1.1.6. Acetate bath

Few authors have been reported on the electroplating of some metals

and alloys from acetate baths [54-57]. Abd El Wahaab et.al [58] studied the

electrodepositlon of nickel from baths containing nickel acetate ba§e

electrolytes under various plating conditions such as bath composition,

current density, temperature and super imposed sinusoidal a.c on d.c. A

detailed study has been made on the influence of these variables on the

potentiodynamic polarization [59]. Cathodic current efficiency of these baths,

bath composition, current density temperature, throwing power and the

surface morphology of the deposits were examined by SEM and crystal

structure by X-ray diffraction studies [60]. Sultan et.al [61] have been studied

the effect of nickel acetate with formamide electrolyte.

The above author have been reported the hardness and structure of

deposits from nickel acetate-N,N, Dimethyl formamide water bath [62]. A

comparison study was carried out Sultan et.al with sulphate and acetate bath

and its hardness, cathode current efficiency and surface morphology [63]. A

nickel chloride - nickel acetate bath was found to provide a suitable solution

for nickel plating on stereotypes. The advantages indicated are high current

density, 40-50 amp/ft^, as well as combination of tensile strength and

hardness [64]. Nickel sulfamate, in conjunction with nickel acetate containing

boric acid, leads to a mirror image bright deposit with 100% efficiency. Nickel

acetate suitably buffers the catholyte solution, leading to an improved

thickness of electrodeposited metal [65]. Electroless depositions of nickel

films from nickel acetate using hydrazine as a reducing agent have been

reported [66]..

37
2.1.1.7. Effect of Additives

The use of organic compounds as addition agents in aqueous

electroplating baths is a fascinating field, owing mainly due to interesting and

important effects produced on the growth and structure and thereby on the

character of the deposit by very low concentrations of the additives in the

bath. The striking effects on electrocrystallization processes of small

concentrations of addition agents point to their adsorption on a high energy

surface and deposition on growth sites. It is for these reasons the effects

seem to be out of proportion to their concentration in the solution [67-78].

The effect of the addition agents on the corrosion resistance have been

studied in detail from the standpoint of the nature of the inclusions

incorporated and from the changed structure of the plate, as well as from

purposeful inclusion in the plate of very finely dispersed non- conducting

particles. The key to modern bright plating was the discovery of the combined

use of an organic "carrier" brightener with an auxiliary organic compound that

produced brightness and leveling In their conjunctive use.

In 1936, the commercial use of an aromatic sulfon-compound

(p-toluene sulfonamide) together with an unsaturated aldehyde as the

brightening system was started. By 1940, it was recognized that unsaturation

was an essential characteristics for the effectiveness of the aromatic sulfon-

compounds and also for the effectiveness of the auxiliary cooperative

brilliancy imparting agents in the production of brilliant, ductile, leveling from

weakly acidic plating baths.

Beach et.al [79] studied the effect of hydroxyl sulfonic compounds and

amine compounds [80], nitrogen containing compounds ethylene and

38
propylene compounds as additives in briglit nickel deposition, either alone or

as a combination of two such compounds.

The effect of saccharin [81] and organic additives [82], kinds of

aliphatic alcohols on the surface morphology and crystal orientation of nickel

plated from Watt's bath have been studied [83], through cyclic voltammetric

studies [84, 85]. Effect of Coumarin [86] and 1, 4-butyene diol [87] was

reported.

2.1.2 Application of nickel electrodeposits from various bath

Electroplating is employed in industry to improve the appearance of

surface, to give the good corrosion protection for the substrate and to improve

the wear resistance etc. [88]. Nickel electroplating is extensively used as a

surface coating technology. The application of nickel electroplating fall into

three main categories; decorative, functional, and electroforming [89]. Nickel

is widely used as a base metal in the process industry because of its excellent

resistance to general corrosion [90].

In recent years, LIGA Ni- micro electro-mechanical system (MEMS)

structures have been developed for applications in high aspect ratio and

thicker devices [91] weapons safety and arming system [91], heat exchangers

[92] and micro gears [92]. Electrodeposition of nickel, combined with laser

lithographic patterning is also used for manufacturing optical recording

devices, including computer CD-Rom drives and music CDS [93, 94].

2.2 Ni-Co Alloy Electrodeposition

Ni-Co alloy, as coatings or bulk alloys have been widely used for

decoration, corrosion resistance and magnetic recording devices, etc. Due to

39
their higher strength, Ni-Co alloys have found wide technological applications

in the electronic, mechanical, petrochemical and medical fields. There are five

basic choice of electrolytic plating processes that can be used to deposit Ni-

Co alloy viz., sulfate, sulfate-chloride, chloride, sulfamate and acetate.

2.2.1 Electrolytes used for Ni-Co Alloy electrodeposition

2.2.1.1 Sulfate Electrolytes

Cobalt has been a favorite constituent of bright nickel plating baths.

The most important of the bright cobalt-nickel plating baths is the one

patented by Weisberg and Stoddard [95] in 1936. Glasstone reported the

basic aspects of sulfate bath [96, 97]. Effect of bath composition, effect of

current density, effect pH, and structures of the deposits are discussed in

detail [98, 99].

The effects of agitation are mentioned in many of the researches on

the electrodeposition of the alloys, but Pletenew and Kusnezowa [100] and

Adilov and Tsyganov [101] made a special study of the effect of rotation on

the cathode on the composition of the deposit. Comparisons of the effects of

plating variables were reported by various investigators [102, 106]. The

properties of Ni-Co alloys containing about 1% cobalt were studied in detail by

Zentner et.al [75]. The properties measured were density, hardness, tensile

strength, elongation. Young's modulus, electrical resistivity, and magnetic

properties.

The alloys were harder than nickel. Those containing more than 20% of

cobalt had hardness about equal to that of cobalt. Lainer [103] measured the

hardness of several alloys. The crystallographic structure and magnetic

properties was studied [104]. The cathodic polarization studies and hydrogen

40
evolution reaction [105] were reported [106-108]. Ni-Co alloy powder

deposition was reported [109]. Structural, magnetic and corrosion properties

of the ternary alloy Co-Ni-Mo were reported in sulfate baths [110,111].

Selective black coating of Ni-Co for solar application was investigated [112].

2.2.1.2. Sulfate-Chloride Electrolytes

The investigations on the electrodeposited Ni-Co alloys have shown

that their microstructure and properties were found to depend strongly on the

Co content, which can be controlled by the experimental parameters, such as

bath composition, temperature, pH value and current density [113-115]. The

effect of plating parameters on the composition and morphology of Ni-Co

deposits were compared in many literatures [116-118]. Golodnitsky et.al.

Recently studied the effects of Co content on the tensile strength, internal

stress and high-temperature oxidation of Ni-Co alloy [114].

Their activities for the oxygen evolution reaction and hydrogen

evolution reaction were also studied on electrodeposited Ni-Co ultra

microelectrodes [119,120]. Cathodic polarization and structure of the deposits

was reported [121,122]. Moreover, much interest is focused on the magnetic

properties of Ni-Co alloys due to the application of these alloys in various

magnetic devices, especially in microsystem technology for manufacture of

sensors, actuators and inductors [123,124]. It is reported that the magnetic

properties of Ni-Co alloy were greatly influenced by the composition and

phase structure of Ni-Co alloy [124]. The composition and microstructure,

mechanical and tribological properties are reported [125]. Magnetic properties

of nanocrystalline iron group alloy were reported from sulfate and chloride

baths [126].

41
2.2.1.3. Chloride Electrolytes

The electrodeposition of Ni-Co alloy is Classified as anomalous [127],

meaning that the less noble metal (Co) is deposited preferentially. The bath

composition and bath parameters were reported in chloride bath [128-13Q].

The cathodic co-deposition of nickel and cobalt carried out using simple

chloride baths were reported [131,132]. The effects of addition of two buffers

have been investigated from chloride bath [133]. The phase structure and

mechanical properties were studied by Duch and Young et.al, [134,135].

Chonglun et.al has been investigated Ni-Co alloy with different electrolytes

and current densities [136]. Pulse plating with different wetting agents was

reported from chloride bath [137].

2.2.1.4. Sulfamate Electrolytes

The bright Ni-Co alloy deposited from sulfamate bath was reported

[138,139]. Certain basic parameters with different anion additives and

mechanical properties of electrodeposited alloy were investigated [123,140].

Myung and Golodnitsky [141, 140] investigated the relationship between the

crystal structure, phase and the corrosion resistance of the alloy. The

properties of the solution conditions and crystal structure for the

electrodeposition of alloy from sulfamate solutions were reported [142-144].

2.2.1.5. Acetate Electrolytes

Deposits from acetate bath are similar to those from sulfate bath but

are useful for high current density operations. The bath compositions, solution

charterstics and surface morphology, crystal structures were reported [145].

Effects of saccharin and sodium lauryl sulphate [146] electrolytes, either with

42
or without the addition of complexing compounds, e.g., pyrophosphate [147]

or citrates [148] were reported. Nano crystalline Ni-Co alloy prepared by high-

speed jet plating [149] was investigated. Ni-Co alloy deposited on aluminum

plate from chloride bath were also reported [150]. The superplastic

mechanisms of the nano crystalline Ni-Co alloy have been discussed based

on the observations of its grain growth and microstructural changes [151].

2.2.2 Applications of Ni-Co alloy

Ni-Co alloy have been investigated as an important engineering

materials for several decades because of their unique properties, such as

high strength, good wear resistance, heat- conductive, high hardness, high

internal tension and particular magnetic properties. Although Ni-Co films are

widely used in protective and decorative plating applications [152] they are

also used as permanent magnetic memories with a high commutations speed

[153]. Additionally, the use of Ni-Co alloys has been extended to the

production of three dimensional, complex- shaped finished components by the

electroforming technique [154].

Moreover, much interest is focused on the magnetic properties of

Ni-Co alloys in various magnetic devices, especially in microsystem

technology for manufacture of sensors, actuators and inductors [155,156]. As

compared to pure nickel, the alloy possesses good adhesion, mechanical

properties, tribological properties, corrosion resistance, themnal stability and

excellent magnetic properties [157]. Ni-Co alloys were also used as catalyst

for H2O2 decomposition [158].

43
 Aim and scope of the present work

Electrodeposition of nickel and its alloys has made rapid strides and is

now extensively used for finishing iron and steel products and widely used for

decoration, corrosion resistance and magnetic recording devices. Production

of chromate conversion coatings on nickel act as a good base for paints and

enhance corrosion resistance.

Hitherto not much works have been reported on electrodeposition of

nickel from an acetate bath, though acetate in often taken as a minor

ingredient in the plating bath. It is of a certain scientific and applied interest to

study the possibility of electroplating of nickel and its alloy from acetate

solution, since the acetate based nickel plating baths are being considered as

made eco-friendly and the deposits to have some advantages like improved

hardness, wear resistance and corrosion resistance over those from other

known nickel plating baths. It was with a view to promote such studies, the

present programme of work was taken up.

Of the numerous alloys, Nickel-Cobalt alloys which have wide industrial

applications have been selected for the study. A detailed study of various

plating parameters would be made with respect to the compositions of the

alloy and their ability to produce deposits of acceptable qualities for their

intended applications. In a similar manner, the selection of addition agents

would be made out of the most commonly used ones in the electroplating

industries. The selection would be made with the caution that the bath

possesses the stability and ability to produce bright deposits with desirable

properties even on long standing. Likewise, the selection of the additives is

44
the most important one to make the deposit commercially acceptable. The

additives/brightener should have (1) stability for the long durations (2)

capacity to produce maximum brightness over a wide current density ranges

(3) no or little influence on the cathode or anode efficiencies (4) good leveling

power and ability to improve throwing power (5) ability to improve the

properties of the deposits (6) no or little influence on the properties due to its

degradation products. The above mentioned criteria would be kept in mind

while choosing the brightener or additive for the plating process.

The present work is to focus on the following aspects of the Ni and Nl-

Co alloy plating process based on acetate bath formulations.

• Hull cell studies for optimizing the current density ranges.

• Marring - Blum cell studies to measure the throwing power.

• Current efficiency measurements to known about the energy

requirements.

• Cathodic polarization studies to understand Hydrogen evolution

reaction and its consequences on the plating process.

• Cyclic voltammetry studies for understating the mechanism of the

deposition process.

*> Weight loss studies, potentiodynamic polarization studies and

impedance methods to evaluate the corrosion behaviour of the nickel

and its alloy obtained in presence and absence of the additives in the

plating bath in 5 % NaCI medium.

• SEM and AFM studies to determine the surface morphology of the

deposits.

• XRD studies to determine phase structure of the deposits.

45
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55
 CHAPTER_
_ ^ . - ^ . . . ^

^''""^^A;^;^
 CHAPTER- ill

EXPERIMENTAL DETAILS

3.1 MATERIALS, CHEMICALS AND INSTRUMENTS USED

Mild steel specimens were used as a base material for the deposition

of Nickel and its Ni-Co alloys. The mild steel specimens were given the

following sequential pretreatment before the electrodeposition.

1. Degreasing with trichloroethylene

2. Alkaline electro cleaning

(2 minutes cathodic following composition)

Sodium hydroxide - 35 g/l

Sodium carbonate -25 g/l

Current density - 7 A/ dm^

3. Washed with running water

4. Mild acid dip in 5 % (v/v) hydrochloric acid for 10 seconds

5. Washed with running water

6. Distilled water dip.

The anode used was a Nickel slab of high purity (99.99%). All the

chemicals used for carrying out the experiments were of analar grade. Triple

distilled water was used for the preparation of solutions.

D.C. Regulated power supply (Aplab) was used as current source for

all deposition studies. The plating cell setup was shown in Fig. 3.1. 1A hot

plate was used for the maintenance of the temperature.

56
3.2 BATH PREPARATION AND PURIFICATION

For any electroplating, proper method of preparing baths and

preconditioning the solutions to remove metallic and other impurities is an

essential part to get good deposits of required physical and chemical

properties.

The plating bath of the following composition was prepared and used in

the investigation for electrodeposition.

Nickel

Ni(CH3C02)2.4H20 25 - 200 g/l

NiCIa 15-60g/l

H3BO3 15-45 g/l

Acetic acid 5 - 20 ml/I

pH 2-5

Current density 0.5 - 5 A/dm^

Temperature 30 - 60 °C

Ni-Co Alloy

Ni(CH3C02)2.4H20 25 - 200 g/l

Co(CH3C02)2.4H20 5 - 40 g/l

NiCl2 15-60 g/l

H3BO3 15-45 g/l

Acetic acid 5 - 2 0 ml/1

pH 2-5

Current density 0.5 - 5 A/dm^

Temperature 30-80^C

57
 •^f -

•
•i •
•- r '*

Fig. 3.1 Plating Cell setup

'vR
3.3 HULL-CELL MEASUREMENTS

A useful method of testing the baths by means of specially designed

plating cell like Hull-Cell, so that one can observe the nature of the deposit

over a range of current densities [1].

The function of this cell is to provide by geometric configuration of a

deposit on a flat surface which reproducibly records the character of the

deposit fomned at all current densities within the operating range. The cathode

specimen is inclined at an angle (38°) to the anode so that by measuring from

the high current density end, the distances of the point spanning the desired

deposit pattern, the values of current densities corresponding to those points

for production of deposits of desired quality can be calculated or obtained

from a curve or from a tabulated data. Polished mild steel cathodes of size

100 X 75 X 1.0 mm and cell currents of 1 A were used. This technique was

used to find out whether a suitable brightener could be used in the case of

Nickel plating and to examine the usefulness of the chosen plating bath

composition and operating conditions. The following formula enabled to

calculate the current density at a desired point on the Hull- Cell cathode.

Current density in A/dm^ at

any point on the inclined cathode = C (5.1 - 5.24 log L)

Where C = total current passing through the cell

L = distance in cm of the point at which current density is

required from the higher current density end of the cathode. This equation

applies to the range 0.64 - 8.25 cm.

59
3.4 CURRENT EFFICIENCY MEASUREMENTS [2]

Mild steel specimens of size 5 x 2cm were mechanically polished and

degreased by using trichloro ethylene. One side of the specimen was masked

with lacquer. The specimens were alkaline cleaned cathodically in the alkaline

cleaning solution for 3-5 minutes. The specimens were then inserted in a 250

ml beaker containing the electrolyte. Pure nickel anode of the same area as

that of the cathode was used. Deposition was carried out at a current density

of 1A/dm^ for one hour using a constant current regulator and held constant

throughout the experiment. A copper coulometer was used to follow the

charge flow in the circuit. After deposition the cathode was removed. Washed

well with distilled water, dried and weighed.

Experiments were carried out both in nickel and its alloy bath solutions

with optimum concentration of the addition agents and without addition

agents. Each experiment was repeated twice with a fresh electrode.

From the difference in weight, the cathode current efficiency was

calculating using the formula

Actual gain
Current efficiency = x 100
Theoretical gain

Thus the influence of additives on the cathode current efficiency was

studied.

Cathode current efficiency for alloy,

Mx100
e X Q
Nl-Co

60
Where, M = Mass of the alloy deposit (g)

e Ni-co = electrochemical equivalent of Ni, Co

Q = quantity of electricity passed in Coulombs (A x Sec)

The electrochemical equivalent of Ni-Co alloy was calculated as

Ni Co

M-Co
(*„i « U + (^co "" ^Nl)

Where, eNi and eco are the electrochemical equivalents of Nickel and Cobalt

respectively; fNi and fco are their respective fractions in the deposit.

3.5 THROWING POWER MEASUREMENTS [3, 4]

The throwing power of an electrolytic cell describes its ability to give

deposition of unifomri thickness over the entire cathodic area.

Standard Haring-Blum cell was used to determine the

percentage of throwing power [5] for nickel plating baths with and without

addition agents. The cell contains a perforated anode and two cathodes, one

placed near the anode and the other at the far end of the anode in the

distance ratio of 1:5. Throwing power was calculated using the known Field's

equation.

L-M
Percentage of throwing power = X 100
L + M-2

Where L is the linear distance ratio and M is the metal ratio. These are

defined as

61
 Distance of a far cathode
Linear ratio (L) =
Distance of near cathode

Weight of deposit on near cathode

Metal ratio (M) =

Weight of deposit on far cathode

3.6 CATHODIC POLARIZATION

The pretreated mild steel specimens (6.25cm^) were subjected to

cathodic polarization studies in the nickel plating baths with and without

additives using a three electrode cell arrangement. The potential of steel

cathode at different current densities during nickel and its alloy deposition of

the above baths were measured Vs SCE and obtained E-l curve.

3.7 CHARACTERIZATION OF NICKEL AND ITS ALLOY ELECTRODEPOSITS

3.7.1 Physico - chemical characterization

Practical electrodeposition is highly diverse in nature and no single

universal experimental procedure is found satisfactory to cover all aspects of

electrodeposition of metals and alloys. However, it is very essential to select

relevant methods to correlate laboratory experiments with actual industrial

operations [1, 2]. Though absolute reproducibility is rather impossible to

achieve due to several factors, reproducibility with minimum error is of

considerable importance. It is therefore desirable to perform experiments in

triplicate. The precautionary measures regarding the size and the shape of

62
the cathode, nature of the cathode surface, design and plating procedures are

necessary to obtain reproducible results.

Surface preparation prior to deposition is an important factor and can

be achieved by mechanical, chemical and electrochemical methods.

The characteristics of the deposits from a plating solution are

influenced by plating conditions, nature of the substrate, composition of the

solution and its purity. The obtained deposits under different conditions were

studied by Scanning Electron Microscope (SEM), Energy Dispersive X- ray

analysis, (EDAX) Atomic Force Microscope (AFM) and X- ray Diffraction

studies (XRD) technique.

a) Adhesion

The adhesion of an electrodeposited coating is an important measure

of its serviceability. The principal causes for poor adhesion are: (1) the

presence of foreign material between the coating and the basis metal, (2) the

presence of a weak layer of metal either upon the surface plated or on the

initial deposit, and (3) the incidence of stress in the deposited metal. Adhesion

testing methods [6, 7] can be broadly classified into (i) quantitative test and (ii)

qualitative test.

The quantitative tests such as Ollard test, Cobalt nodule test and Peel

test require a thick deposit, which is time consuming. Hence, it is not suitable

for testing of thin coatings actually used in service conditions.

The qualitative tests are simple and have some significance for the

practical plater, but are of little value for precise specifications. Operations

63
which can be included in this category are bending, twisting, bufTing, abrading,

chiseling, filling cupping and thermal cycling.

One of the simplest methods, known as the bend test [8] was followed

here to evaluate the adhesion of zinc, coatings on mild steel. Mild steel

specimens (5 x 5 x 0.1 cm) were plated with the respective metals and were

then bent at 180°, repeating the bending upto the point of fracture of the steel

base.

b) Porosity
Porosity of electrodeposited coatings can be defined as the degree of

uncovered microscopic regions of the base metal [9, 10]. In general the

degree of porosity of a deposit decreases with increasing thickness. Porosity

is however important in the case of deposits which are more noble than the

basis metal since in such coatings the rate of attack at the pores is likely to be

accelerated. Traditional and reliable tests for porosity are based on the

application of a reagent which will react with the basis metal through pores in

the coating and yet will not attack the deposit itself.

For determining the porosity of coatings of nickel and its alloy on mild

steel substrates the Ferroxyl test was used [11]. The Ferroxyl solution was

one of sodium chloride (50g/l) and white gelatin (50g/l), dissolved in distilled

water at 45 °C. Filter paper strips of 25 x 25 mm area each were impregnated

with the above solution and dried. Before testing the porosity, the filter paper

piece was placed at different locations on the plated surface. After 10 mins.

the papers were removed and placed at once in 10 g/l solution of potassium

ferricyanide. The porosity of each deposit subjected to this test, the test

specimens were degreased, electrocieaned and dried.

64
c) Microhardness measurements

Hardness of the electrodeposits nickel and its alloys surface with

various additives was measured using a LECO Microhardness Tester Model

M400 by the static indentation method [12]. A diamond pyramid was pressed

into the deposit under a load of 50 gms for 15 seconds and the indentation

diagonal measured after the load was removed. Each electrodeposit used for

this measurement was of ZQ\im thickness. The microhardness in Kgmm"^ was

determined in each case by using the formula.

HV= 1854 xUd^

L being the load applied in grams and d the diagonal of the indentation in

micrometers.

d) Abrasion resistance

The abrasion resistance was determined using a Taber Abraser Model

503 as per AASTMD - 4060. The specimen was weighed initial and

mounted on the turn tabe of the instrument. It is then subjected to abrasion by

using Cs-10 abrading wheels for a load of lOOOg for 1000 cycles. The

specimen was then reweighed and the weight loss (in mg) observed is

expressed as the abrasion (index) resistance.

e) Friction and wear loss

The tribological behaviour was tested on a reciprocating ball-on disk

UMT-2MT Tribometer (USA) at room temperature with relative humidity of

45-55% under dry sliding conditions. Mild steel ball (diameter 4mm with

hardness of RC 62) was used as the counter body; all tests were performed

under a load of 3N with a sliding speed of 55 mms\ The friction coefficient

65
and sliding time were recorded automatically during the test. The wear volume

loss was measured using a surface profilometer, wear rates of all the alloy

deposits were calculated using the equation of K= V/SF, where VA is the wear

volume loss in mm^, S is the total sliding distance in m and F the normal load iruN.

f) Reflectivity

The principle of a gloss meter is based on the measurement of the

specular component of the reflected light. The intensity of reflected light is

measured in a specific angle range. The measurement of the gloss value Rs is

a relative measurement. The measurement results are related to a highly

polished, black glass standard with a defined refractive index of 1.567. The

black glass standard has an assigned specular gloss value of 100

(calibration). In order to obtain comparable results, the measurement device

and operation have been defined in international specifications [13-16].

The nickel deposits of 10 pm thickness obtained from various baths

(8 X 5 X 0.1 cm) were subjected to reflectivity measurement using a gloss

meter referenced against a aluminium optical block, the reflectivity for which

was arbitrarily set at 99.8% at an angle of 85°. The measurements were

carried out at different points of the coatings surface.

3.7.2 Weight loss Studies

For weight loss studies, the deposit was obtained on a mild steel panel

of size 5 X 2cm from the bath containing different addition agents. The coated

specimens were immersed in 5% NaCI solutions by using glass hooks. After

the test period of 24 hours the specimens were removed, rinsed in typical

cleaning solution, dried and weighed. The weight loss was determined and

66
the corrosion rate (R) in mpy was calculated. The icorr for nickel corrosion was

calculated using the equation.

2v r a t wtof element 1
Uorr WAJ cnn^) = a i 2 8 I — „ ^ I mpy
L valence xdensity J

For the alloy,

, , 2\ T a t wUif element 1
Icorr ( [ l A / Cm^) = 0.128 — — ^ ^
L valence xdensity J
X (percent of element in aHoy) xmpy

3.7.3 Potentiodynamic polarization studies

For polarization studies Nickel deposit was obtained on the mild steel

electrode of area 1 cm^ from the bath containing different addition agents at

their optimum concentrations. A rectangular platinum foil was used as the

counter electrode. Saturated calomel electrode was used as the reference

electrode. A 5% NaCI solution was used as the test solution. Polarization

studies were done from +200mV to -200mV with respect to their rest potential

at a scan rate of 10mV/sec.

The E Vs. log I plots were made from which the corrosion current and

corrosion potential were calculated.

3.7.4 Impedance measurements

The EIS experiments were carried out at the D.C deposition potential

with superimposed AC voltage of amplitude 10 mV in the frequency range of

100 mHz to 100 KHz using EG&G impedance analyzer, Model 6310 Software

Model M270. The coated Nickel and its alloy and platinum foils were used as

the working and counter electrodes respectively. The SCE was used as the

reference electrode. The 5% NaCI solution was used as the electrolyte

medium. The photograph of the system is shown in Fig. 3.2. The real part (Z')

67
and the imciginary part (Z") of the cell impedance were measured at various

frequencies. Impedance measurements were carried out both for Nickel and

its alloy baths with the optimum concentration of the additives that give bright

deposits. From the impedance diagrams the charge transfer values and

double layer capacitance values were calculated.

3.7.5 Cyclic Voltammetry

Cyclic voltammetry studies were carried out with BAS 100 WB

Electrochemical analyzer. The photograph of the system is shown in

Fig. 3.3. For the CV studies, a platinum foil was used as the working electrode

and large area of Pt foil used as the counter electrode. Saturated calomel

electrode was used as the reference electrode for both Nickel and its alloy

baths.

Cyclic Voltammetry studies were done at different scan rates. The

sensitivity of the system was adjusted by 1 mAA/. The range of scanning

potentials -1000 mV to 200 mV and -1200 to 400 mV for nickel and its alloy

baths respectively.

3.7.6 UV studies for bath characterization

The nickel and its alloy complexes in solution were identified using

ultraviolet-visible spectroscopy using a Shimadzu-UV-visible-2401

spectrophotometer. In these experiments, the spectra were recorded after

filing a standard quartz cuvette (cell path length of 1.0 cm) with the particular

electrolyte, and absorbance was recorded at a fast scan over the wavelength

range of 200-500 nm. The quartz cuvette was rinsed and dried after each

scan before filling it with the next solution. The UV spectra of the nickel and its

alloy bath were measured.

68
Fig.3.2 Electrochemical Impedance analyzer

69
Fig. 3.3 BAS 100 W6 Electrochemical analyzer

70
3.7.7 Scanning Electron Microscope

Mild steel specimens of size 2.5 x 5 cm were polished and degreased

by trichloroethyiene. Then the panels were alkaline cleaned and one side of

the panel was nnasked. The other side of the specimen was plated with nickel

deposit of 30vim thickness in the baths in presence and absence of the best

concentration additive.

From the plated specimen a small area was cut and examined at

magnifications of x2500 & x5000 using scanning electron microscope.

3.7.8 Atomic Force Microscope (AFM)

Atomic force microscopy (Digital Instruments Nanoscope E) (AFM) was

used to check the surface morphology of the nickel and its alloy.

3.7.9 X-ray Diffraction (XRD)

The crystal structure of the nickel and its alloy deposit grains was

examined through X- ray diffraction. The deposits produced with and with out

additives were studied. The samples were scanned between 30° -100° (29) at

a scan rate of 1 degree per minute using Cu Ka (X=1.5405 A°) radiation. The

peaks due to the different phases were identified and the corresponding

lattice parameters also calculated. The particle size of the deposit is

computed from,

Dhki = kX / (p cos 0)

Where k is Scherrer constant with the value of 1, X- ray wave length X-

(1.5405 nm for Cu target), 0 Bragg angle, and p peak half-width in radiation unit.

71
''^^ERENCES
References

1. Nohse (Walter) (Ed) Investigation of Electroplating and related solutions

with the aid of Hull cell, Robert Draper Ltd., Teddington (1966).

2. N.V. Parthasarathy (Ed) Practical Electroplating Hand Book, Prentice Hall,

New Jersey, (1989).

3. H. Silmen, G. Isserlis and A.F. Averill, Finishing Publications Ltd.,

Teddington, England (1978) p.6.

4. S. Shawki, F. Hanna and Z.A. Hamid, Metal Finishing, 85, (1987) 59.

5. B.E. Conway and J.O'M. Bockris, Plating, 46 (1959) 371.

6. D. Davies and J.A. Whittaker, Metals and Materials, 1.2 (1967)

7. H. Plog, Galvanotechnik, 61 (1970) 155.

8. ASTM Test method B571-84, Adhesion of metallic coatings (1995).

9. J.K Dennis and T.E Such (Ed), Nickel and Chromium plating

Buttenvorths, London, (1986).

10. L.J Durney (Ed) Electroplating Engineering Handbook. 4*'' edition. Von

Nostrand Reinhold, New York, (1984).

11. ASTM Test method B689-81, Electroplated Engineering. Nickel coatings,

American Society for testing and materials, (1985).

12. ASTM B578-87, (Reapproved 1993) Standard Test Method for

Microhardness of electrodeposited coatings, (1995).

13. ASTM D523-89, Standard Test method for specular gloss.

72
14. Japanese Industrial Standard JIS Z 8741 (1983), Method of measurement

for specular glossiness.

15. DIN 67 530 (1982), Reflektometer als Hilfsmittel Zur Glanzbeurteilung^^

abenen Anstrich-Und Kunststoffoberflachen.

16. Gabriele KIgle-Boeckler, Byk-Gardner Inc., Silver Spring, Md. Metal

Finishing, 5 (1995) 28.

73
(^••^ •••te
 CHAPTER-IV

RESULTS AND DISCUSSION

4.1 STUDIES ON NICKEL DEPOSITION

Nickel acetate is a well known bath component in the electroplating of

nickel and its alloys. It produces bright and smooth unifomn fine grained

deposits.

The eco-friendly nickel acetate salt bath was chosen as an alternative

for sulphate bath, chloride bath and phyrophate bath. Detailed investigations

were carried out by varying bath constituents such as nickel acetate, nickel

chloride, boric acid, and acetic acid with different additives. The influence of

temperature on the plating process at the optimized plating condition is

followed.

4.1.1 HULL CELL STUDIES

4.1.1.1 Effect of bath constituents
a) Effect of Nickel acetate

The effect of addition of varying concentrations of nickel acetate in

nickel plating bath at a cell current of 1 A and at 30 °C is presented in

Fig.4.1.1 and the Hull cell patterns employed are shown in Fig 4.1.0. It may be

seen from Fig.4.1.1 (a-e), with the increasing concentrations of nickel acetate

from 25 g/l to 200 g/l, the quality of the deposits over the current range is

varied. At lower concentrations upto 50 g/l, semi bright, dull and bright

deposits are obtained. Above this concentration ranges, only dull and bright

deposits alone are obtained. Further it is noted with increased acetate

74
 I I I l"^"^^"-*^

MIRROR BRIGHT DEPOSIT

BRIGHT DEPOSIT
.....>..>.t

SEMI BRIGHT DEPOSIT

' ' '.^ '.I '.I'.» '.* '.t '.*',•. '.!•<•.

.\\\\\\\\\\\\\\\\\V\NV

UN PLATED DEPOSIT

POWDERY DEPOSIT

MATTEY WHITE

NON UNIFORM DEPOSIT

DULL DEPOSIT

BURNT DEPOSIT

.••••••••••< PITTED DEPOSIT

BLACK DEPOSIT

GREY DEPOSIT

Fig.4.1.0 Legend for Hull Cell Studies

75
 Nickel Acetate g/L

a. 25

b. 50 yiryyyyyy^^

c. 100 rZ-Z-
< < < 4 < < < < 4 < < < « 4 < < « 4 4 4 < < 4 4 < < < < 4 4 < < < <

d. 150 1 4 4 4 « 4 « < 4 < < 4 4 4 < 4 4 4 4 * 4 4 < 4 < < « ( 4 4 4 < * <

4 4 < 4 4 < < < 4 4 4 < < 4 4 < 4 4 4 4 < < 4 4 < 4 < 4 4 4 4 4 < 4
e. 200 ,>,> » > > > > > • » > > » > > > » > > > > > > > > > > » » > > > > >
4 4 < < 4 4 4 « 4 4 < < 4 4 < 4 4 < 4 4 4 4 4 4 < 4 < < 4 4 4 < 4 4
>

1 1 1 1 1 1 1

1.S 1.0 0.1

HCD A/dm' LCD

Fig.4.1.1 Effect of Nickel acetate concentration

Nickel chloride g/L

a. 0 .4 4 4 < « < 4 4 4 < < 4 1 4 < « 4 4 4 « < < < « « < < 4 4 4 < 4 4 4
•^' 4 < « < < < < 4 < 4 4 4 4 « 4 4 4 4 < < < « « < 4 4 4 4 4 < < 4 4

b.lS

c. 30

d.45 • * > * > > >

4 4 4 4 4 4 4 4 4 4 4 4 4
' 4 4 4 4 4 4 4 4
> * > > > > >
4 4 *<.«.«.« 4 < « < < <
- - 4 4"4'4"4'4'«"4"4'4" 4'4"4'«'4'*"€

e.60 .4 4 4 4 < 4 4 « 4 4 4 4 « 4 4 4 4 4 4 4 4 4 4 < <

4 4 4 4 < « 4 4 4 4 4 4 4 4 « 4 4 < 4 4 4 4 4 4 4

J_ _L
1.5 1.0 0.1
HCD LCD
A/dm

Fig.4.1.2 Effect of Nickel chloride concentration

76
concentrations, the current range over which bright deposits obtained is

increased. At an optimum concentration of 150 g/l over the entire range of

current densities there is a complete bright deposit only. This is the pattern at

200 g/l also.

b) Effect of Nickel Chloride

The addition of nickel chloride is expected to enhance the conductivity

of the bath besides ensuring uniform dissolution of the anode [1]. The effect of

addition of nickel chloride, between the ranges 0 and 60 g/l is tried in the bath

containing the optimized concentration of 150 g/l nickel acetate and the

results of the Hull Cell pattern is presented in Fig.4.1.2 (a-e). At lower

concentration of 50 g/l nickel chloride, at high current ranges say above

1.5 A/dm^, a matty white finish nickel deposit was observed, whereas at lower

current density ranges, a semi bright deposit was obtained. The same is the

case with 30 g/l of nickel chloride, in the high current ranges but at lower

current ranges non-unifomi deposits were noticed. With 45 g/l and 60 g/l of

nickel chloride additions, over a wide range of current densities say between 1

and above 4 A/dm^, bright deposits were observed. On the lower cunrent

density ranges only non- uniform deposits were obtained. Thus, benefit of

addition of nickel chloride can be realized by operating the plating cell at

higher current density ranges say above 1 A/dm^. This is a welcome feature only.

c) Effect of boric acid

The effect of varying the concentration of boric acid in a nickel plating

bath containing nickel acetate 150 g/l, nickel chloride 45 g/l is shown in

77
 Boric acid g/L
a. 0 <<<<<<< *.***<*^ *<<<<*<
<><»< >< >< >< »< > > > > *><» <^ <» *><»<><> <> *><»* >< »<><»<>
77?77^77?????7?r=-=^ •.-fc!W5-!5-S-!M
b. 15
'm^^^m^^-^mm;<mMi
c. 25

d. 35 < <k <k<1< i < »< »< >< 1< >< »< k< ^< k<. i< k< ft< <k . >< <> <k <1
» 1 >

«. 45 _i._t A . i .4 t t < < t < < < < < < < < « <

1.5 1.0 0.1

HCD A/dm LCD

Flg.4.1.3 Effect of Boric acid concentration

Acetic acid mi/L

a. 0 ************ <*<*********<
.•' ''.^ •'.* •'.* -V-V •'} ••/ •',

b. 5

c. 10

d. 15 > >>> > »>>>)'.

> > » > > > • ;
< 4
1^
e. 20

±. ±
1.5 1J) 0.1
HCD A/dm LCD

Fig.4.1.4 Effect of Acetic acid concentration

78
Fig.4.1.3 (a). With 15 g/l boric acid, a uniform semi bright deposit was

obtained between 1.5 A/dm^ and 4 A/dm^ and below 1.5 A/dm^ a non- uniform

coverage and dull deposits were noticed Fig.4.1.3 (b). Further addition of

boric acid to 25 g/l, gave a semi bright deposit between 1.25 A/dm^ and

4 A/dm^. Below 1.25 A/dm^ current densities, only dull and non-uniform

deposits were observed. However with 35 g/l concentration of boric acid and

above, bright deposits over a wide range of current densities say between

1.25 A/dm^ and 4 A/dm^ were obtained. At lower current densities ranges as

in the earlier cases, only dull and non-unifomn deposits were observed. A

similar trend was observed with further increase in concentration of boric acid

to 45 g/l. But of course the current densities over which bright deposits

appeared are slightly narrowed down. The appearance of dull and semi bright

deposits were as in the previous cases. This is an optimized concentration of

35 g/l of boric acid could be recommend. The role of boric acid in the nickel

plating bath will also help to maintain the pH of the nickel plating bath by

acting as a buffer [2, 3]. Thus enhance in the stability of the bath.

e) Effect of Acetic acid

The effect of varying the concentrations of Acetic acid in a nickel

plating bath containing nickel acetate 150 g/l, Nickel chloride 45 g/l and boric

acid 35 g/l operated at 1 A cell current for a duration of 10 minutes at 30 °C is

given in Fig. 4.1.4(a). From the Figure 4.1.4(b), it may be seen that with the

introduction of 5ml of acetic acid a uniform semi bright deposit was obtained

at the current density above 1.8 A/dm^. A dull deposit and non- uniform

coverage were noticed below 1 /Vdm^. Further addition of acetic acid to

79
10 ml/I produced a semi bright deposit over a wide range of current densities

as shown in Fig.4.1.4 (c). With an enhanced addition of acetic acid to 15 ml/I

the nature of the deposit improved to a considerable extent to produce

uniform bright deposits over almost the entire area of the Hull cell plate in the

current density ranges 1.25 to 4 A/dm^, shown in Fig. 4.1.4 (d). Addition of

acetic acid to 20 ml gave the same smooth bright uniform deposit as with

15 g/l ie. Fig.4.1.4 (e). From the above studies, it may be concluded that

15 ml/I acetic acid is favorable for nickel plating.

4.1.2. Effect of current density, temperature and pH on the appearance of

the deposit.

Acetate nickel plating bath of composition mentioned in the

experimental section has been chosen and with this bath the operating

parameters were varied to ensure maximum bright, good adherent and pore

free deposits could be obtained.

Table 4.1.1 gives the effect of current density on the appearance of the

deposit. A dull deposit is obtained at the current density of 0.5 A/dm^ and

uniform bright deposit is obtained with a current density of 1.0 A/dm^ to

2.0 A/dm^. It may be concluded that bright and good adherent deposits could

be obtained in the current density ranges of 1.0 A/dm^ to 2.0 A/dm^ and not

below that. At still higher current densities black powdery appearance of the

deposits were perceived.

Uniform and bright deposits were obtained at the temperature of 40°C

and at higher temperatures only porous and semi bright deposits were

obtained. The results are shown in Table 4.1.2.

80
Table 4.1.1 Effect of current density on the appearance of the deposit at
temperature 30 °C and pH 5

Current Density
Appearance of the deposit
(A/dm^)
0.5 Dull deposit
Bright
1.0
Bright
2.0
3.0 Bright and semi bright

4.0 Bright, semi bright and black

5.0 Powdery and burnt deposits

Table 4.1.2 Effect of temperature on the appearance of the deposit at

current density 1 A/dm^ and pH 5

Temperature °C Appearance of the deposit

30 Semi bright and Dull deposit
40 Bright
50 Bright and semi bright
60 Semi bright and black

Table 4.1.3 Effect of pH on the appearance of the deposit at current

density 1 A/dm^ and at Temperature 40 '^C

pH Appearance of the deposit

2 Non- unifomi coverage
3 Semi bright and Dull deposit
4 Bright and semi bright
5 Bight adherent deposit

81
Table 4.1.4 Nomenclature, molecular formula and structure of additives

used in this study

Nomenclature Molecular Molecular Structure

Formula Weight

Saccharin C7H4NS03Na 205.17

0^0

Dextrin (CeHioOs)/ (CsHioOs)/

1,4-butyne diol C4H6O2 86.09 Clt-C = C-CH_

1^ 12
OH OH

Coumarin C9H6O2 146.15

CO-
SO3H

1,3-naphthalene CloHe 2SO3H 289.24

suiphonic acid

82
 The effect of pH on the appearance of the deposit is shown in

Table4.1.3. Bright and good adherent deposits were obtained at pH 5. At

lower pHs say below 3, the nature of the deposit obtained is semi bright, non-

unifomn and dull.

4.1.3 Effect of Additives

The nomenclature and molecular formula of the additives used in this

study is given in Tabie 4.1.4. The effect of various additives were studied in

the optimized nickel bath of composition containing nickel acetate 150 g/l,

nickel chloride 45 g/l, boric acid 35 g/l and acetic acid 15 ml/I and operated at

a cell current of 1 A and at a temperature 40 °C.

a) Effect of Saccharin

The concentration of saccharin was varied from 1 g/l to 4 g/l. The

corresponding Hull cell patterns are presented in Figures.4.1.5 (a-e). In the

case of saccharin at 1 g/l concentration 3 semi bright, dull and bright deposits

were observed. As the concentration was increased to 2 g/l the quality of the

deposit was mirror bright in the current density ranges below 2 A/dm^. Above

this current density bright deposits were observed. At a higher concentration

of saccharin, powdery, bright and semi bright deposits were obtained.

b) Effect of Dextrin

The Hull cell patterns obtained for the additive dextrin of different

concentrations are shown in Figures 4.1.6 (a-e). The optimum concentration

of the additive in the bath was 3 g/l, where a bright deposit at the current

density range of 1.5 to 4 A/dm^ was obtained. With increase in concentration.

83
Saccharin g/L
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i i J < < I 1 i t 1 < •>>p;--.'--;'-;i•.••••••••••'••.••-I

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Fig. 4.1.5 Effect of Saccharin concentration

dextrin g/L

a. OJ) s« «sss%sss\sssss\ssssssss .v^:-.;:-;:-:;.vi-:-:-

' - - ' • • ' ' . . . ' . . . . . . . I.. •••• ••••i

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*******

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d.3.0 » » > > >
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)

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• » » . » » » » » > » * * * * _ « , _ _ _ _
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e.4.0 4 < 4 4 4 4 4 4 <

4 < < 4 < < < 4 4

X J_

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HCD A/dm LCD

Fig.4.1.6 Effect of Dextrin concentration

84
1,4-Butyn8clioimi/L
a. 0.0 r < ^ < < < ^ ^ « < « ' * < « ^ ^ 4 * * ^ ^ < f . - . . . - y . J.. :...;, • - -

\ \ \ % \. %•' .•'« t I 1 1 « »

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> * > > t L * •- •• •- .* •. •• •..' •. •• •. •• •..' •- .• •. .• •-.' • 1
> > > > 1 ''^Mi^'^' ••-•'-•'-••-••*

c.2.0 »'>>>»»»>»> *.*.* I » » » I r I

.»<><»<>*><>* »<>
*''''*' «i I I I < < < < I 1 « < ff

ci.3.0

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wmm
±. ±.
2 2 1.5 \A 0.1
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Fig.4.1.7 Effect of 1, 4-butyne diol concentration

Ceumarin fl/L
« 4 4 « 4 < < < < < < < < < < 4 < < < < < < « '

a. 0.0 >I-I-
• > > > > > > > > > > > >

b.1.0 4 « < < < f < < « 4 < < <

•;y^^-^V\^^^

i i i f i i f i i f r •r v f - f r T i i i i f i i
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. < < « 4 « > > > > > > > »

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*'*'*'*'"*'^<^*"^"'^

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HCD A/dm' LCD

Fig.4.1.8 Effect of Coumarin concentration

85
1,3 -naphthalene
sulphonic acid g/i
' , > > > > » > > » > » > > > > > > » » > > > » .•.•;.•.•.•.•.•.•.•;.•;.•,.__
< * < < < < < * < < < < < < < « < < < < < < < < •.•,•.••.•.•.*.•.••.•.•.'.•___

a. 0.0
• • • • • < i^fmyfyr
b.1.0

c.2.0

d.3.0

e.4.0
_L _L _L X I J

4 3 2 15 1.0 0.1
HCD A/dni LCD

Fig.4.1.9 Effect of 1, 3- naphthalene sulphonic acid

Concentration

86
bright and dull deposits were observed only at high current density areas and

non-uniform deposit zones in the low current density end.

c) Effect of 1,4- Butyne diol

The concentration of 1, 4-Butyne diol was varied between 1.0 ml/I and

4.0 ml/1. The Hull cell results of the plating bath are shown in

Figures.4.1.7 (a-e). The optimum concentration of the additive in the bath was

3.0 ml/I, a bright deposit was observed in the current density range of 1.2 to

4.0 A/dm^. For this concentration at low current density ranges, a black

deposit was obtained. With further increase in the concentration of the

additive, a decreased length of bright deposit was observed with narrowed

down current ranges (1-1.75 A/dm^) with high current regions yielding burnt

deposits.

d) Effect of Coumarin

1.0 to 4.0 g/l Coumarin concentrations have been tried in plating bath

and the results are presented in Figures 4.1.8 (a-e). With 2.0 g/l concentration

of the additive in the bath bight deposit could be obtained in the current

density range of 0.7 to 4 A/dm^. For the highest concentration of 4.0 g/l, a

black and burnt deposit was noticed covering the current density range of

1.8 to 4.0 A/dm^. In the low current density regions there were only dull

deposits.

e) Effect of 1, 3- Naphthalene sulphonic acid

The Hull cell patterns obtained for the additive 1, 3- naphthalene

sulphonic acid is shown in Figures 4.1.9 (a-e). The concentration range of

1.0 g/l to 4.0 g/l was tried with the plating bath. The optimum concentration

was found to be 2.0 g/l with which only semi bright deposit was observed over

87
the current density range below 3 A/dm^. With other concentrations mostly

powdery, semi bright or burnt deposits only obtained. It is noted that this

additive is not useful to give bright deposits.

4.1.3.1 A comparative account from Hull cell studies on different

additives

In the absence of any additive, a bright deposit was observed in the

narrow current regions when compared to the addition of brighteners to the

plating bath. The additives are helpful in getting an increased bright length,

semi bright, dull or burnt deposits which are adherent and pore free. Further

the operational current density to get such deposits was also found to be

widened covering lower to higher current densities. The presence of additives

in plating baths has shown to influence the physical and mechanical

properties of the deposits such as grain size, brightness, internal stress,

pitting and even sometimes the chemical composition [4, 5]. It is predicted

that the additives get adsorbed onto the electrode surface partially and cause

decrease in the number of available active sites and controls the nucleation

and growth step of the deposition process resulting in control of the grain size

and refinement [6]. Of all the controlling factors known, addition of organic

additives to the plating bath is the best. The order of perfomnance among the

additives to give bright deposits over a wide range of current densities,

particularly at higher current densities is given below.

Saccharin > Coumarin >1, 4 -butyne diol > Dextrin > 1, 3 -naphthalene

sulphonic acid.

-^ Decreasing order of performance.

88
 Thus the performance of the above additives reflected in the Hull cell

studies should be related to the basic adsorption process and in turn with their

molecular structures of the adsorption site. The best perfomnance of

saccharin could be due to the expandable valency of sulphur atom in the five

membered ring that could be facilitate co-ordination with adsorbed metal

cation prior to the discharge reactions giving rise to energetic pathways. The

very poor perfomiance of 1, 3 naphthalene sulphonic acid could be due to the

deactivation of benzene ring by the two electron withdrawing sulphonic groups

hindering adsorption and co-ordination to metal cations. The presence of

hydroxyl groups which could chelate with metal cations could account for the

perfomriances of dextrin and 1, 4- butyne diol. The absence operation of

strong electronic effects in the case of the molecule Coumarin could explain

its lack lusture performance. The perfomnance and mechanism of

electrodeposition process in the presence of additives will be discussed at the

end of this chapter.

4.1.3.2 Influence of operating parameters on the performance of the best

additive. (Hull cell studies)

It was found that saccharin was the best additive in the bath where in

we could get mirror finish deposits. The effect of operating parameters such

as temperature and pH were studied for the baths in presence of the optimum

concentration of the additive. The Hull cell pattern for the temperature effect is

presented in Figures.4.1.10. (a-d)

With increase in temperature the mirror bright deposits change into

bright deposit with narrowed current density ranges. At a maximum of 60 °C a

semi bright, powdery or black deposit only obtained. Thus it is concluded that

89
the additives give the best performance at the ambient temperature only. At

elevated temperatures the faster thermally aided transport hinders the grain

refinement and impedes the nucleation rate resulting in poor quality deposits.

The influence of pH is presented in Figures 4.1.11 (a-d). The pti

studies were confined to acidic conditions only because of stability problem of

the bath. At pH 5, it is possible to get bright deposit over the full range of

current densities 1 to 4 A/dm^. At highly acidic pHs, semi bright or no deposits

were observed. In the near neutral of pH 5, H* or OH" concentration of the

bath may help in stabilizing surface concentration of the additive which in turn

controls the quality of the deposit.

90
Temperature °c

a. 30 < ><><><><> > > > <> <> >< >< >4 >
>>>>>>>>>>>>>>

b.40
. . 4 < < < 4 4 < . 4 4 4 4 4 4 4 4
*>>*>**>
>>»>»»
' - ' - * - • • • •
4 4 4 4 4 4 4 4 4 4 4 4 4

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d.60 *. ' • • •.•• '.*• • •• • *. • •• •,*• • / • • '• •.•• • •• • •• • •• • •• '.*• • / • • . ' • *.'• • •• 'I
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Fig.4.1.10 Effect of temperature on the performance

of Saccharin in the nickel acetate bath

pH
;•.•*••••.•••.*•'

a. 2 p.v.v.\--.v-.».
^•ir\ \ % ^ ^ % \ \ * \ % %^ \ % '
4 4 4 4 4 4 4 4 4 4 4 < < < « < 4 - i\\\NVSVS,\VS
b.3 4 4 4 4 4
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. 4 4 4 4 < < 4 4 4 4 < < 4 4 4 4 4 4 < < 4 4 .WAWsW
• •!•/.* .V* V* •'
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-*-'•-''-'*-'•-'•-
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'*'**'
» > > > » 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 .. .
d.S 4 4 4 4 4 4 4 4 4 4 4 4 4 4 . 4 4 4 4 4 4 4 4 4 4 ••

2 2 1-5 1J) 0.1

HCD A/dm LCD

Fig.4.1.11 Effect of pH on the performance of

Saccharin in the nicltel acetate bath

91
4.1.4 Cathode Current Efficiency Measurements

It is. often noted that the additives added to plating baths help in

improving very much the quality of the deposits, but at the same time resulting

in some loss of cathode current efficiency. Hence to understand how for-the

additives tried affect the cathode current efficiencies, the present investigation

was taken. Values of cathode current efficiency of the baths in the presence

of various additives at different current densities are given in Table 4.1.5. The

addition of additives to the plating baths have not decreased the cathode

current efficiencies but only have slight positive effect. The cathode current

efficiency gradually increased upto 2 A/dm^ and then slightly decreased from

3 to 5 A/dm^. This may be due to the evolution of hydrogen gas at the high

current densities. Generally it is reported that the efficiency increased with

current density and then leveled off upto a certain critical value, beyond which

tree formation is resulting. In the present investigations too with high current

density of 5 A/dm^ some tree fomnation in the edge of the deposits could be

noted. The plating rate observed with these additives is in the range of 28-

35|jm/hr at 2 A/dm^ current density in the bath. With increasing applied

current density the deposition rate of nickel increase primarily because of the

reduction of H* becomes transport limited. All the additives are seen to

perform well as for as cathode current efficiency performance is concerned.

Still the best plating rate is observed with Saccharin. High plating rate and

current efficiencies will tell upon the economy of the plating process.

92
4.1.5 Throwing Power Studies

Throwing power of the bath was calculated for plain bath and in

presence of the various additives, the results are presented in Table 4.1.6.

Using some, new buffering components like malonic, succinic, gluteriic.

Tartaric and Citric acids in Watt's bath it is reported that the throwing power of

the bath was in the range 61-72 [7]. Electrochemical investigations on the

influence of electrolyte composition of Watt's baths with special regards to

throwing power has been made by Wehner et.al using citric acid, tartaric acid,

mannite, sodium dithionite potassium disulfite, sodium hypophosphite, sodium

phosphate and Dimethylamine borane (DMAB). It was investigated that the

throwing power decreases in the following order: DMAB> sodium

hypophosphite> citrate> tartaric acid > mannite> potassium disulfite. The

throwing power range was around 28 [8]. In the sulfate-oxalate bath throwing

power was reported to be in the range of 35 - 45 [9] and for pyrophosphate

bath it was 46 [lO], Watt's bath 25 [10] and a chloride bath 33 [10]. A

comparative account of throwing power values are reported for nickel and

chromium by Sobha Jayakrishnan et.al [11]. The throwing power of the

acetate bath investigated presently is found to be quite impressive compared

to the throwing power of many of the other reported baths. Even without the

additives the throwing power of the acetate bath is quite high. The influence of

the additives with regard to throwing power is seem to be minimal. However,

these additives do not have any adverse effect but only, slightly improve the

throwing power for all the current densities. As with eariier studies, here also

the best performance of saccharin is registered.

93
 Table 4.1.5 Current efficiency of Nicltel acetate baths in
presence of various additives

Current efficiency (%)

S. NO Name of tlie
additives Current density (A/dm^)

0.5 1.0 2.0 3.0 4.0 5.0

1 plain 90 93 94.5 92 85 82

2 Saccharin 95 97 97.5 94 90 85

3 Dextrin 93 96 97.0 93 89 86

4 1,4-butynediol 94 96 97.5 91 87 84

5 Coumarin 92 95 97.0 94 89 82

6 1,3-naphthalene 93 96 96.5 93 88 81
suiphonic acid

Table 4.1.6 Throwing power of Nickel acetate baths in presence

of various additives

Throwing Power {%)

Name of the
S.No additives
Current density (A/dm^)
1 2 3 4

1 Plain bath 49.2 51.9 53.1 54.3

2 Saccharin 52.1 52.9 54.2 56.7
3 Dextrin 51.0 51.9 52.7 54.3
4 1,4-butynediol 51.4 52.2 53.0 54.8
5 Coumarin 51.9 52.7 53.8 55.0
6 1,3-naphthalene 52.0 52.5 53.4 54.7
suiphonic acid

94
4.1.6 Cyclic Voltammetry studies

Cyclic Voltammetry is one of the most powerful electrochemical

techniques used as a means of obtaining a quick electrochemical spectrum of

a charge transfer reaction mechanism. It has been proved to be valuable m

the study of surface process, such as the formation and reduction of oxide

layer on metal surface and in electrodeposition process.

Electrochemical behaviour of Ni in sulphate and chloride baths have

been studied by various authors [12, 13], through cyclic voltammetry analysis

and the wealth of infonnations have been obtained. Since acetate baths have

not been well and widely studied, the cyclic voltammetry studies for nickel

deposition with this bath in presence of additives through cyclic voltammetry

studies is expected throw much light on the mechanism of the deposition

process.

4.1.6.1 Effect of Sweep Rate

Figure 4.1.12 presents the cyclic voltammogram obtained Ni in acetate

bath in the absence of additives at various sweep rates. It was evident that as

the sweep rate increases, both deposition and dissolution peaks occur at

higher negative and positive potentials respectively. The charges flowed

under the peaks also increased with increase in sweep rates. The

dependence of cathodic peak current on the scan rate is presented in

Fig.4.1.13. The linearity between log current vs log scan rate proves the

reduction process to be under pseudo-diffusion control. The slope of the

above plot is noted to be 0.53 accordingly to Randless Sevcik equation. The

95
electrolytic deposition of nickel on to paraffin impregnated electrode from

nickel chloride bath has been reported to be one of diffusion controlled

process [14].

4.1.6.2 Effect of Chloride ions

Figure.4.1.14 (a) illustrates the effects of chloride ions on thfe

deposition characteristics of nickel. The magnitude of the stripping peak has

increased with increase in chloride ion concentration. This is due to the fact

that chloride ion acts as an active corrodant and hence favours dissolution.

The deposition current has decreased with increase in the addition of chloride

ions and this may be due to the specific adsorption of chloride ion on the

surface. Similar observation has been reported in the study of quantification of

additives in a Watt's nickel bath by the cyclic voltammetric stripping technique [12].

4.1.6.3 Effect of Nickel ions

Figure 4.1.14 (b) shows a cyclic voltammogram which depicts the

effect of Ni^* ions on the deposition characteristics of nickel. As the

concentration of Nickel acetate was increased from 0.3 to 0.5 M in the

electrolytic solution, the deposition increases evident from increased cathodic

peak currents. Similarly the charges under the stripping peaks are also

increased as is nonnally expected. The high concentration of Ni^* ions in

solutions causes the deposition process to be kinetically favoured but not

thenriodynamically evident from the negative shift of cathodic peak potentials.

However, for the anodic process it is both kinetically and thermodynamically

favoured suggested by the less positive shift of the anodic peak potential.

96
4.1.6.4 Effect of pH

Figure 4.1.15 presents the electrochemical spectrum obtained in

different pH solutions at 100 mV/s. The electrode was polarized from

+100 mV to -1000 mV, the fonward scan exhibited a broad cathodic peak

at -710 mV in pH 3. During the reverse scan an anodic peak was seen

at -290 mV in pH 3 solutions. Anodic peak currents decreased with pH.

Increase of pH caused decrease the cathodic peak cun'ents and the peak

potential becoming noble suggesting that the lower pHs are more favourable

for reduction. This is also intune with the proposed mechanism, wherein the

Rate determining step is followed by a step which involves H"" as the reactant.

Further at lower pHs, the hydrogen evaluation potential is shifted to more

negative value indicating enhanced plating rate.

4.1.6.5 Role of additives in Niclcel plating bath

The deposition and dissolution charterstics of Ni^* ions in the absence

and presence of the additives at their optimum concentration at a scan rate of

100 mV/s is given in Table 4.1.8 and in Fig. 4.1.16. It is observed that the

introduction of the additives into the nickel plating bath has not changed the

electrochemical spectrum, in the sense that there is only one anodic and one

cathodic peak appearances. But in presence of the additives both the anodic

and cathodic peak potentials have been altered. The cathodic peak currents

are unifomnly increased with the presence of the additives, indicating that the

additives increased the deposition rates. Among the additives saccharin is

noted to be the best, giving maximum cathodic peak current and less negative

peak potential. Also in the presence of the compounds the hydrogen evolution

97
rate is marginally diminished with negative shift of the hydrogen evolution

potential.

The favourable effect of the additives in the deposition process could

'1'
be explained in terms of adsorption of the molecules in the interfadS •ilhd

complexation of the metal cation thus controlling the activity of the metal

cations resulting in lesser energy requirement for the reduction process.

There is no blocking effect of the additives on the active sites of the electrode

as some times encountered [15]

The positive anodic peak potential in the case of the plain bath

indicates the spontaneity of the anodic reaction while a negative shift of peak

potentials obtained with the additives are illustrative of their inhibitive nature

for the metal dissolution process which has been confirmed from the corrosion

studies.

Based on the results obtained from cyclic voltammetry, the following

mechanism appears to be most suitable for nickel deposition [16].

Ni^^ + H2O <-> NiOH^ + H* (1)

NiOH* + e" —>• NiOHads (rate-detemiining step) (2)

NiOHads+ H*+e- O - Ni +H2O (3)

98
4.1.6.6 Effect of Saccharin at different scan rates

Figure 4.1.17 depicts a typical cyclic voltammogram on Pt electrode in

Ni acetate bath with saccharin the best of the additives of different sweep

rates. The Cyclic voltammetry parameters are calculated and presented in

Table 4.1.7. The Diffusion Co-efficient and the Heterogeneous Rate Constant

are in the same order for cases with out and with the presence of the

additives in the bath indicating that the kinetics of the deposition process is

not significantly altered. However, the change in transfer coefficient value has

been altered indicating that the additive is able to cause a symmetrical

potential barrier than in their absence.

Table 4.1.7

Effect of scan rate on cyclic voltammetric parameters for

the deposition of nickel on Pt electrode

Electrolyte Diffusion Standard Transfer

Coefficient Heterogeneous Coefficient
X 10^ cms"* Rate Constant (scan
(D) XlO-'cms"^ independent)
(ks) (an)
Plain 2.72 8.90
3.30 1.86 0.842
3.84 3.07
Saccharin 3.74 6.47
4.10 9.06 0.577
4.14 11.60

99
 0.03

0.02

0.01 —

a 0 —

-0.01

-0.02

-800 -400
Pc3t©ntial (mV)

Fig.4.1.12 Cyclic voltammogram on platinum electrode

in Ni acetate bath at various sweep rates,
a) 50 mV b) 100 mV c) 150 mV

1.4

y=0.5320x+0.649B
F?= 0.9978

"a
!=• 1.2
9

— I —

1.5 1.7 1.9 2.1 2.3

log(ir)

Fig.4.1.13 Dependence of log ip*^ on log of scan

rate from CV studies of Ni acetate bath

100
 0.04 —

<
E

fc
3
o

0 —

-0.04

-800 -400
Potential (mV)

Fig. 4.1.14 (a) Cyclic voltammogram on platinum electrode

in Ni chloride of various concentrations.
(a)0.1M(b)0.2M(c)0.3M

101
 0.04

0.02 —\

0 ^
<
E

t
3
-0.02

-0.04

-0.06

-800 -400
Potential (mV)

Fig. 4.1.14(b) Cyclic voltammogram on platinum electrode

in Ni acetate of various concentrations.
(a) 0.3M (b) 0.4 M (c) 0.5 M

102
 0.01

0 —

<
E
c
<D

o -0.01

-0.02

-0.03

-800 -400

Potential (mV)

Fig.4.1.15 Cyclic voltammogram on platinum electrode

in Ni acetate bath of various pHs.
(a) 3 (b) 4 (c) 5

103
 0.02

<
c

-0.02 —

-400
Potential (mV)

Fig.4.1.16 Cyclic voltammogram on platinum electrode in Ni acetate

bath with different additives at a scan rate of 100 mV/s
(a) Plain (b) Saccharin (c) Dextrin (d) 1,4-butyne diol
(e) Coumarin and (f) 1, 3-naphthalene sulphonic acid

104
 0.02 —

<
E
•D

-0.02

-400
Potential (mV)

Fig.4.1.17 Cyclic voltammogram on platinum electrode in Ni

acetate bath with saccharin at different scan rates,
(a) 50 mV (b) 100 mV (c) 150 mV

105
Table 4.1.8 Cyclic voltammetric results obtained on platinum electrode
in Nickel Acetate bath at a scan rate of 100 mV/s obtained with optimum
concentration of different additives

Dissolution Peak Deposition Peak

Name of ttie
additives •p ^p
(mV) (mA) (mV) (mA)

Plain 74 29.10 -595 3.48

Saccharin -175 9.73 -568 5.17

Dextrin -54 27.94 -575 4.09

1,4-butynediol -66 13.97 -575 4.18

Coumarin -35 22.90 -574 5.07

1,3-Naphthalene -47 17.80 -590 4.93

sulphonic acid

106
4.1.7 Cathodic Polarization lUleasurements

4.1.7.1 Cathodic Polarization

Polarization increased witli current density. Good throwing power is

expected only when deposition takes place with a high concentration

polarization. All polarization increasing factors generally have a favourable

effect on the throwing power of baths. Hence increase in temperature, degree

of agitation, bath composition, current density and electrolyte conductivity

have resulted in improved throwing power. The relation between current

density and current efficiency is also a detemnining factor for the throwing

power. Figure 4.1.18 gives the results for the cathodic polarization behaviour

with different additives. For all the additives cathodic peak potentials are

shifted to more negative values indicating the energy barrier for the deposition

process.

Among the additives saccharin containing bath exhibited a situation

where the cathodic potential was shifted to more negative values compared to

others. This may attributed to the fact that saccharin is more polarized at the

cathode surface. Higher the polarization, stronger is the adsorption of the

respective additives on the active sites of the cathode surface. This could

explain the lowering of current efficiency at higher concentration of the

additive. The slope of cathodic polarization curve in the Tafel from, is seen to

give the experimental slopes to be 0.123, 0.124 V / dec for the plain bath as

well as with the best additive saccharin added bath, respectively. These

values are in confimnation with the proposed mechanism suggested which

gives rise to a theoretical slope of 0.12 V/ dec.

107
Fig.4t1.18. Cathodic polarization curves for nickel deposition
from acetate bath (a) Plain, (b) Saccharin, (c) Dextrin,
(d) 1,4-butynediol, (e) Coumarin and
(f) 1, 3-naphttialene sulphonic acid

108
4.1.8 Physical Properties of the Nickel Deposit
a) Adhesion
One of the known simplest methods, bend test was followed to

evaluate the adhesion of nickel deposits. Deposits were made on mild steel

substrate to a thickness of 25 pm under various operating conditions. The

plated specimens were bent to 180°. Bending was repeated several times

upto the point of fracture of the steel substrate. No flaking or peeling off the

deposits was seen when observed with an optical microscope under low

magnification. The deposits were found to withstand the bend showing that

the keying of the deposit to the base metal was very good in the case of the

deposits obtained with and without the additives in the plating bath.

b) Porosity

Ferroxyl test was carried out to indicate the presence of pores if any in

the deposits. Deposits were made on mild steel substrates for 7, 11, 15 and

19|jm thickness. Absence of blue spots revealed that all nickel electrodeposits

were non-porous even for 7 pm thickness.

c) Microhardness

The Microhardness of the electrodeposited acetate based nickel

deposits were obtained from plain bath and in presence of various additives at

various temperatures and applied load of 100 grams. Figure 4.19. Shows the

variation of microhardness and the deposits obtained from various baths at

different temperatures. The effect of temperature of the plating solution on the

hardness has been studied [17]. It is reported that a minimum hardness of

deposits formed at intermediate temperatures. In general, sulfate ions

decreased the hardness of the electrodeposits but amino-, thio and nitro

109
compounds increased the hardness of the electrodeposits [18]. The increased

hardness in the case of the deposits obtained from baths containing additives

when compared to plain bath has been noted for all the temperatures. The

additives are adsorbed in the cathode surface as a colloidal basic salt. Thus

colloidal basic salts (hydroxides of nickel) may increase the hardness by

being adsorbed and subsequently included in the deposits, thus inhibiting the

growth of crystals [19] and it acts to obstruct the movement of dislocations

and resist the plastic flow of the matrix thus improving the hardness. In the

case of Dextrin the hardness was found to decrease with increase of

temperature. The decrease in microhardness at higher temperature in the

case of dextrin added baths can be attributed to the increase in grain size.

The ions are more mobile at higher temperatures which favour equilibrium

deposition and the fonmation of larger grains with a low free energy. In the

case of dextrin at the maximum temperature 60 °C of the bath, the hardness

of the deposit was found to be decrease than that obtained from plain bath.

600-1
—•—a.Plainbalh
^ 575- —•—b.Saccharin
ok
—X—cDexWn
g 550H -A-d.1,4-Biieneclol
—»-e.Coumaiin
I 525i -•—f.1,3-napMhalen
sulphonicacid
500 —r—
20 30 40 50 60 70
Tempeature "C

Fig.4.1.19 Effect of Hardness on Temperature of the bath

110
d) Reflectivity
Reflectivity of tiie deposits depends upon the brightness, grain size and

structure of the coatings. The percentage of brightness was measured by

using a gloss meter. Brightness is directly related to the surface structure^of

electrodeposits.

Among the additives Saccharin shows the high reflectivity (82%)

compared to deposits obtained with other additives. The fine grain size was

probably caused by growth inhibition which was due to the co-deposition of

sulphonyl compounds. The reflectivity of Coumarin is (78%), 1, 4-Butyne diol

(65%) , 1,3 -naphthalene sulphonic acid(62%) and Dextrin(52%). The order

of the reflectivity offered by them are as follows:

Saccharin > Coumarin > 1, 4-Butyne diol > 1, 3 -naphthalene

sulphonic acid > Dextrin

e) Wear Loss

The wear loss for nickel and additives both in the as plated and heat

treated conditions are given in table 4.1.9.

Wear is a surface phenomenon which consists of the gradual materials

deterioration of contacting surfaces. Here the abrasive wear is the removal of

particles due to friction.

In the case of all the additive systems it was observed that there is an

increase in the wear resistance compared to the pure nickel. The wear

resistance of the additives after heat treatment was found to increase

compared with the one under as plated condition. Among the additives

developed, the wear resistance of saccharin system is the highest, with a

minimum wear loss of 22.5 mgs after heat treatment.

Ill
4.1.9 Corrosion resistance characteristics of the nicltel deposits

4.1.9.1 Weight loss measurements

The corrosion behaviour of nickel from plain bath and from additives

added baths in 5 % NaCI was noted through weight loss method and the

results are presented in Table 4.1.10. 15-20% HCI or 10% H2SO4 has been

used until the removal of corroded product formed from the surface at room

temperature [20]. Among the different additives, the corrosion resistance

behaviour is in the following order: saccharin > 1, 4-butyne diol > Coumarin >

dextrin > 1, 3-naphthalen sulphonic acid. The trend of corrosion inhibition Is

related to the micro structure of the deposits. Except dextrin all the additives

have showed the grain refinement and compactness in the deposits. This

accounts for improved corrosion resistance behaviour. In the case of dextrin

deposits, some porosities are observed which is evident from SEM studies

and this might have resulted in slight enhanced corrosion.

4.1.9.2 Potentiodynamic polarization measurements

Figure 4.1.20 shows the potentiodynamic polarization curves for pure

nickel and that obtained in presence of the additives in 5% NaCI. The linear

segments of the polarization curves were extrapolated to OCP to obtain the

corrosion current density (Icorr)- The corrosion results obtained from

potentiodynamic polarization method is summarized in Table 4.1.11.

The corrosion current for the deposits obtained from baths carrying all

the additives have decreased, when compared to the deposit nickel obtained

from plain bath In the absence of any additive. It shows that deposits from

additive added baths offered improved corrosion protection in 5% NaCI

solution. In all these cases, the cathodic control of the corrosion reaction is

112
 Table 4.1.9 Wear loss of electrodeposits Nickel Deposits

Wear Loss (mgs)

SL.No System As plated condition after heat treated condition

1 Plain 38.5 25.4

2 Saccharin 31.5 22.5

3 Dextrin 35.3 24.1

4 1,4-Butynediol 33.4 21.3

5 Coumarin 34.5 23.3

6 1,3-Naphthalene 34.7 23.6

sulphonic acid

Table 4.1.10 Weight loss measurements for nickel deposits in 5% NaCI

with optimum concentration of different additives

Additive Corrosion rate Icon-

(mpy) (fiA/cm^)
Plain 3.8x10-^ 1.60x10-^

Saccharin 3.0 xlO"^ 1.27x10-^

Dextrin 3.2x10-^ 1.35x10-^

1,4-Butynediol 1.6x10-^ 6.8x10-^

Coumarin 2.1 X 10-^ 8.7x10"*

1,3-Naphthalene 2.2x10"^ 9.2x10-^

sulphonic acid

113
le'

-858

E (nU)

Fig.4.1.20 Potentiodynamic polarization curves in 5 % NaCI

solution for electrodeposits obtained from nickel
acetate bath with different additives
(a) P>ain(b) Saccharin (c) Dextrin(d}1, 4- Butyne diol
(e) Coumarin (f) 1, 3- naphthalene sulphonic acid

114
 1 I I 1 1 1 1 r

15.1

J.-
M
•.888

-5.888

I I J I I I I I
1Z.58 ZZ.S8 3Z.S8 IZ.St 52.58
8.88 28.88 18.88 68.88 88.88 188.88 128.88 1«.88
ZK(alM) Zre (OIM)
(a) (b)
1 1 1 1 1 1
18.88 38.88 -
•1

28.88 -
28.88

18.88
8.88 / JL^ _ • •

8.(8 /
-28.88 -

1 1 1 1 1 1
-18.88 18.88 38.88 58.88 78.88 98.88 118.88
8.88 ».(• 28.88 38.88 18.88 58.88 88.88 78.1
2 K (atn)

(C)

V 1 1 1 \

18.88 8
_ 38.88
•

28.88
28.88 .
, I
i 18.88
•
/•"
8.88
8.88
/

1 1 1 1 1 -18.88
8.88 28.88 18.88 68.88 1.88 188.88 128.(
5.88 25.88 15.88 (5.88 85.(
Z K (Ida)
are (Ota)
(e) (f)

Fig.4.1.21 Nyquist plot for nickel deposits from acetate bath with different
Additives (a) Plain (b) Saccharin (c) Dextrin (d) 1,4-butyne diol
(e) Coumarin and (f) 1,3-naphthalene sulphonic acid

115
Table 4.1.11 Potentiodynamic polarization results for nickel deposits in
5 % NaCI with optimum concentration of additives

Name of the Ccorr 'corr ba be

additives (mV) X lO"* (A/cm^) (mV) (mV)
Plain -449 5.2 42 54

Saccharin -680 2.2 96 120

Dextrin -648 3.9 57 68

1,4-Butyne diol -668 3.6 60 65

Coumarin -494 2.9 23 29

1,3-Naphthalene -457 3.8 40 57

sulphonic acid

Table 4.1.12 Impedance measurement for nickel deposits in 5 % NaCI

with optimum concentration of different additives

Name of the Rt Cd. 1 •corr

additives (Ohms) (pF/cm^) (A/cm^)

Plain 38 5.3x10"=* 2.70x10"*

Saccharin 132 1.5x10-^ 4.56x10-''

Dextrin 77 5.7x10-^ 1.75x10-*

1,4-Butyne diol 45 2.4x10"* 3.01 X 10-*

Coumarin 106 1.7x10-' 4.61 X 10-=*

1,3-Naphthalene 50 3.9 xlO-" 2.04x10"*

sulphonic acid

116
inferred from the fact that Ecorr is shifted to the more negative direction. Nickel

plating bath containing saccharin additive gave very low Icorr value, suggesting

the good corrosion protection behavior of the resultant deposit.

4.1.9.3. Impedance method

The results of impedance measurements for nickel deposits from plain

and additives treated baths are given in Table 4.1.12 and in Figure 4.1.21.

The increase in Rt values for the deposits from additives added baths

compared to plain bath show that the deposits have very good corrosion

resistance in the medium. The same trend was observed in weight loss and

polarization measurements. The Cdi values have decreased for all the

deposits indicating lesser charge in the interface. The Nyguistian plots in all

the cases are semicircles confinning the charge transfer control of the

corrosion process. But in the case of dextrin, there is a rising portion at the

low frequency end suggesting a partial mass transfer control [21]. In the case

of dextrin, two semi circles could be seen with the smaller one on the lower

frequency end. This suggests the adsorption of the ions of the medium on the

pores of the deposits in a slow process. Epelboin found evidence for the

following reaction mechanism in which the rate-detennining step (RDS)

involves an intermediate species postulated to be (NiOH)ads [22].

Ni^* + H2O <-> NiOH + H*

NiOH^+ e —> (NiOH)ads (RDS)

(NiOH)ads + H* + e" ^> Ni + H2O

117
Fig.4.1.22 SEM photographs of Ni deposits from acetate
bath at different Magnifications (a) Plain bath
(b) Saccharin (c) Dextrin added baths

118
Fig.4.1.22 SEM photographs of Ni deposits from acetate
bath at different Magnifications (d) 1, 4- Butyne diol
(e) Coumarin (f) 1, 3- naphthalene sulphonic acid
added baths

119
 I ^ 200.0 iim t HISO.OIUD

100.0 iim TS.Oiim

0.0 itm '0.0 |im

(a)

ISO.Oiun 2S00(ini

7S-0|un 1»jO|m

0.0 |im 0.0 (an

« _ 150.0 iini ZSOjOtMi

7S.0|iin 128A|ni

0.0 |im 0.0 |«n

Fig.4.1.23 AFM photographs of Ni deposits from acetate

bath at different Magnifications (a) Plain bath
(b) Saccharin (c) Dextrin (d) 1,4-Butynedlol
(e) Coumarin (f) 1, 3- naphthalene sulphonic acid
added baths

120
Fig.4.1.24 XRD pattern for nickel deposits from
(a) Plain bath (b) Saccharin added bath.

121
4.1.10 Structural investigation of the nickel electrodeposits

4.1.10.1 Surface morphology of the deposits

The optical micrographs of nickel deposits from plain as well as from

additives added baths were taken at different magnifications. The

photomicrographs of the deposits are shown in Figures 4.1.22(a-f)

respectively. From the figures it is clear that, all the additives in the bath are

able to control the morphology of the deposits. Of all the additives the

saccharin exhibits marked influence on the morphology of the nickel

electrodeposits by controlling the grain growth. This may be ascribed to the

inhibitory effect of saccharin on the nickel ion reduction [23].

Coumarin, 1, 4- Butyne diol and 1, 3-naphthalene sulphonic acid

additives are also able to cause fine grained and pore free even deposits. The

behaviour of dextrin seems to be little porous in nature. I

i
4.1.10.2 ARM Studies j

The surface morphology of the electrodeposited nickel from baths with

and without additives was studied by using AFM and the images are

presented in Fig. 4.1.23 (a-f). It clearly reveals that there is a disappearance

of grain boundaries which implies that the formation of amorphous structure

with additive metal atoms unifomnly spread over the substrate. Diameter of the

particles is about 150- 250 |am. The size and shape distribution is quite

homogeneous. It is most apparent that these additives cause of the

agglomeration of smaller particles with saccharin bath giving fine grained

structure.

122
Fig.4.1.24 XRD pattern for nickel deposits from (c) Dextrin
(d) 1, 4- Butyne diol added baths

123
Fig.4.1.24 XRD pattern for nickel deposits from (e) Coumarin
(f) 1, 3- naphthalene sulphonic acid added baths

124
4.1.10.3. XRD studies

Figures 4.1.24 a-f show the X-ray diffraction pattern under as-plated

conditions of the nickel deposits obtained in presence of saccharin, dextrin,

1,4-butyne diol, Coumarin and 1,3- naphthalene sulphonic acid additives-in

the bath. The X-ray diffraction pattern of nickel shows the characteristics

peaks for nickel. The relationship between crystal orientation of nickel and

bondability were investigated. Some of the films consisted of nickel crystals

with a (200) preferred orientation. In general, plated nickel films with relatively

low tensile stress tend to exhibit a (200) preferred orientation [24]. Addition

agents are effective in increasing the cathode potential and had the ability to

decrease the crystal size of the deposit or to alter the type and/or degree of

preferred orientation [25]. With the presence of 1, 3- naphthalene sulphonic

acid, Coumarin and 1, 4- Butyne diol additives in the baths a new peak (222)

are obtained for the deposits. Scherrer analysis reveals that the coherently

diffracting domains have dimensions in the range 20- 50 nm in all the cases.

The calculated parameters for the nickel deposits suggest that the

nature of the deposit is crystalline and face centered cubic (fee) with

a= 3.5238, b= 3.5238 and c= 3.5238.

125
REFERENCES
References

1. W.I. Lajner, N.T. Kudriaweew, Podstawy Galwanostegii, Vol. I, PWT,

Warsaw, 1955, p.314.

2. J. Jl, W.C. Cooper, D.B. Dreisinger and B. Peters, J. Appl. Electrochem.,

25 (1995) 642.

3. Y. Tsuru, M. Nomura and F.R. Foulkes, J. Appl. Electrochem., 32 (2002)

629.

4. J.K. Dennis and J. Fuggle, Electroplat. Metal Finishing., 20 (1967)

370.

5. G. Trejo, H. Ruiz and Y. Meas. J. Appl. Electrochem., 31 (2001) 685.

6. L. Mirkova, G. Maurin, I. Krarter and C.Tsvetkova J. Appl. Electrochem.,

31 (2001)654.

7. yu. D.Gamburg.M.yu. Grosheva, S. Biallozof, M. Hass, Surface and

Coat. Technol. 150 (2002) 95.

8. S. Wehner, A. Bund, U. Lichtenstein, W, Plieth, W. Dahms and

W.Richtering, J. Appl. Electrochem. 33 (2003) 457.

9. A.J. Steiger, Metal Finishing, 57 (1959) 52.

10. S.K. Panikkar and T.L. Rama Char J. Electrochem. Soc, 106 (1959)

494.

11. Sobha Jayakrishnan, et.al.. Trans IMF., 76 (1998) 90.

12. S.Mohan, R. Venkatachalam, N.G. Renganathan and C. Rajeswari

Trans IMF, 79 (2001)73.

13. R. Albalat, E. Gomez, C.Muller, M. Sarret and E.Valles J. Appl.

Electrochem., 21 (1991) 709.

126
14. M. Supicova, R. Rozik, L. Trnkova, R. Orinakoalova, J.Solid State

Electrochem, 10(2006)61.

15. C. Gao, Y. Lu and R. Liu Plating and surface finis., 84 (1997) 83.

16. A.S. Reintjes and M. Flasischmann, Electrochim. Acta, 29 (1984) 557..

17. F.J. Roehl, Monthly Revii .Am. Electroplaters Soc, 34 (1947) 1129.

18. Grincevichene, R. Vishomirskis, S. Jakobson, B. Williams & T. Stasivk,

Metal Finishing, 93 (1995) 10..

19. S. Nakahar and B.C. Felder J. Electrochem. Soc, 129 (1982) 127.

20. Hand Book of Electrochemistry Supplement to Transactions of the

SAEST, 22, NO. 4. (1987)17.
21. M. Holm and T.J. Okeefe J. Appl. Electro chem., 30 (2000) 1125.

22. I. Epelboin and R. Wiart, J. Electrochem. Soc, 118 (1971) 1577.

23. Y. Nakamura & N. Kaneko, M. Watanabe, H. Nezu J. Appl. Electro

Chem. 24(1994)227.

24. Y. Tsuru, R. Takamatsu and K. Hosokawa, J. Surf. Finish. Japan 44

(1993)39; 45(1994)82.

25. Claypon C. Rotoh & Henry Leitheiser, JR. J. Electrochem. Soc, 100

(1953) 553.

127
4.2 STUDIES ON ELECTRODEPOSITION OF Ni-Co ALLOY

Ni-Co alloy, as coatings or bulk alloys have been widely used for

decoration, corrosion resistance and magnetic recording devices, etc. Due to

their higher strength, Ni-Co alloys have found technological applications in the

electronic, mechanical, petrochemical and medical fields. In earlier section

nickel deposition from acetate bath has been discussed exhaustively. Using

that optimized nickel acetate bath, the nickel-cobalt alloy deposition has been

attempted. The present study was carried out in the plating bath containing

150 g/l nickel acetate, 45 g/l nickel chloride, boric acid 35 g/l and acetic acid

15 ml/1. Bath optimization, throwing power, cathode efficiency, alloy

composition, potentiodynamic polarization and impedance studies have been

conducted to understand the alloy plating process and to evaluate the

deposits.

4.2.1 HULL CELL STUDIES

4.2.1.1 Effect of bath constituents

a) Effect of Cobalt acetate

The effect of varying the concentrations of cobalt acetate in Ni-Co alloy

plating bath when operated at a cell current of 1 A and at 30 °C is presented

in Fig. 4.2.1a. With 5 g/l cobalt acetate addition, a non unifonn deposit region

was observed below 1.2 A/dm^. Above this current density region bright

deposit was obtained (Fig.4.2.1b). With the addition of cobalt acetate of 10 g/l

a bright deposit resulted in the current density ranges 1.5 to 4 A/dm^, below

this current density region only semi bright and non uniform deposits were

obtained (Fig.4.2.1c). Further increase in concentration of cobalt acetate to

128
15g/l the bright deposit was observed in the region of current density 1 to

4 A/dm^ and at low current density ends there was a senni bright deposit

(Fig.4.2.1d). With cobalt acetate concentration of 20 g/l the bright deposit

region was narrowed to high current density regions only (above 3 A/dm^)

below that we get only grey coloured deposits (Fig.4.2.1e).

4.2.1.2. Effect of current density, temperature and pH on the appearance

of the deposit

Ni-Co alloy plating bath of composition mentioned in the experimental

section has been chosen and with this bath, the operating parameters were

varied to ensure maximum bright and good adherent and pore free deposits

realized. Table 4.2.1 gives the effect of current density on the appearance of

the deposit. A semi bright and dull deposit was obtained at the current density

range of 0.5 A/dm^ and uniform bright deposit was obtained with a current

density of 1.0 A/dm^ to 2.0 A/dm^. It was found that bright and good adherent

deposits could be obtained at the current density of 1.0 A/dm^ to 2.0 A/dm^

and not below that. At still higher current densities grey appearance of the

deposits were perceived.

Uniform and bright deposits were obtained at the temperature of 40 °C

and at higher temperatures only porous deposits with semi bright appearance

were obtained. The results are shown in Table 4.2.2.

The effect of pH on the appearance of the deposit is shown in

Table4.2.3. Bight deposit and good adherent deposits were obtained at pH 5,

and at lower pH 3, the nature of the deposit was semi bright, non-unifonn

coverage and dull in nature.

129
Table 4.2.1 Effect of current density on the appearance of the deposit at
temperature 30 °C and pH 5

Current Density
(A/dm^) Appearance of the deposit
0.5 Semi bright and Dull deposit
1.0 Bright
2.0 Bright
3.0 Bright and semi bright
4.0 dull and grey
5.0
Powdery and burnt deposits

Table 4.2.2 Effect of temperature on the appearance of the deposit at

current density 2 A/dm^ and pH 5

Temperature °C Appearance of the deposit

30 Semi bright and Dull deposit
40 Bright
50 Bright and semi bright
60 Semi bright and grey

Table 4.2.3 Effect of pH on the appearance of the deposit at current

density 2 A/dm^ and at Temperature 40 °C

pH Appearance of the deposit

2 Non- uniform coverage
3 Semi bright and Dull deposit
4 Bright and semi bright
5 Bight adherent deposit

130
Cobalt acetate g/l
» > > 7 > > > > > > > > > > > > > > > » > > > > > ) _ _ _ _ _ _ V*w~v
a. 0 • C 4 < < - { - t < 4 4 4 < 4 4 4 4 < < 4 4 1 4 ' ( 4
^ > > > > > > > > > > > > > > > > » * ' > > > > »
4 4 _ _ _ _ _ _
» 1 _ _ _ _ _ _
V^'V^v'
*/**/*v

b. 5

c.10

d.IS > » » > > > > > > > > > >

1 4 4 4 4 1 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4
> » > > > » » > > » > > '.••*.••.•.•.•.•".•.•.•.•.-.•.•.•.•.•:

.•.•.•.•.-'.•.*••.•.•,•.•%•,•.•.
< 4 4 « < 4 1 4 < 4 4 4 4 < 4 4 4 4 4 4 i 4 4 4 4 .••.••.••.•*.••.-.••••••.'••.

e. 20 >44>44 >44 ><< >44 >44 >44 ><4 ><< >

_L _L JL.

1.S 1.0 0.1

HCD LCD
A/dm

Fig. 4.2.1 Effect of Cobalt acetate concentration

Saccharin g/L

a. OJ) >> »>>>»>>»>»»»>>»»>>

4 4 » 4 < 4 4 4 4 4 < < « < < < i ^ i < 4 <
4 < > 4 < < 4 < 4 4 4 4 < < 4 4 < < < 4 < 4
W^M^MB.
b. 1JI
.^ -.-.
t;^;>^^;^;'^j

L X J_
4 1.5 1.0 0.1
HCD A/dm LCD

Fig. 4.2.2 Effect of Concentration of Saccliarin

131
 Dextrin g/L

a. 0.0 mmmmm^m
b. 1.0 mm^m^m^yyyy;^;ry;rm
C.2J)

d.3.0

e.4.0
_L
1.5 1,0 0.1
HCD A/din LCD

Fig. 4.2.3 Effect of Concentration of Dextrin

1,4-BulynediolmLil
a.OJ)
i\^</<-/</<-/<-/->/<

b.lJ)

J I
4 1.5 1.0 0.1

HCD A/dm LCD

Fig. 4.2.4 Effect of Concentration of 1,4- butyne diol

132
 Coumarin g/L

a. 0.0
W^$^$^
b. 1.0 <*»*,<,<,<,<,<,<,*,< 4 4 4 4 « 4 4 4 4 < 4 4
r-r-T-t-r"-

C.2J)

d.3.0

e.4.0
X J L J I 1
4 2 1-5 1.0 0.1
HCD A/dm LCD

Fig. 4.2.5 Effect of Concentration of Coumarin

13- naphthalene sulphonic acid g/L

a.OJ) > * > * > > >^> > » > » > > > » » > » »
4 4 > < 4 4 4 4 < 4 4 4 4 4 < 4 « « « < 4 4
jJ..J'../..i'..^J..,J..J'..

b. 1J)

C.2JI

d.3J)

e.4i)
_L J I
4 15 1.0 0.1
HCD A/dnf LCD

Fig. 4.2.6 Effect of Concentration of

1,3- naphthalene sulphonic acid

133
4.2.2 Effect of additives

a) Effect of Saccliarin

The concentration of saccharin was varied from 1 to 4 g/l in the

optimized acetate Ni-Co alloy plating bath. The corresponding Hull .cell

patterns are presented in Fig. 4.2.2. In the case of saccharin added bath with

2 g/l concentration a mirror bright deposit was observed in the current density

region above 1 A/dm^ and below 4 A/dm^. At low current density region the

deposits obtained were dark grey in nature. As the concentration of saccharin

was increased, the deposit obtained were found to be dull, grey and burnt in

nature.

b) Effect of dextrin

The concentration range of the additive tried was between 1.0 g/l and

4.0 g/l. The Hull Cell results of the bath are shown in Fig. 4.2.3. The optimum

concentration of the additive in the bath was 3 g/l when a bright deposit for the

current density range of 0.8 A/dm^ to 2.5 A/dm^ was obtained. With increase

in concentration powdery deposits only at high current density areas and no

deposit zones in the low current density end were realized.

c) Effect of 1,4-butyne diol

With butyne diol the concentration tried between 1ml dm"^ and

4 ml dm'^, the Hull Cell patterns for the plating baths are shown in Fig 4.2.4.

At the additive concentration of 1ml to 2ml dm"^ burnt deposit and dull

deposits was observed in high current region. And further increase in

concentration causes mostly dull, burnt and semi bright deposits for the full

length of current densities.

134
d) Effect of Coumarin

The concentration of Coumarin was varied between 1 g/l and 4g/l in the

alloy plating bath. The results are presented in Fig. 4.2.5. With low

concentration of 1 g/l a bright deposit covering a wide spectrum of the current

density range starting from 1.0 A/dm^ to 4 A/dm^ and above was obtained.

With the increase in concentration of the additive the situation moves on to

bright, semi bright and burnt deposit regions.

e) Effect of 1,3-naphthalene suiphonic acid

1 g/l to 4 g/l concentrations have been tried in the Ni-Co alloy plating

bath and the results are presented in Fig.4.2.6. With 3 g/l concentration we

get a bright deposit in the current density range of 1.0 A/dm^ to 1.8 A/dm^.

With further increase in the concentration of the additive only burnt and semi

bright deposits for the entire current density ranges were obtained.

4.2.2.1 Cathodic current efficiency and composition of Ni-Co alloys

The cathodic current efficiency (CCE) of Ni-Co alloys deposited from

acetate baths is 99% as a result of simultaneous hydrogen non evolution. The

effect of bath composition and some plating parameters on the overall

cathodic current efficiency for the alloy deposition, as well as on the Co

content in the deposit percentages were analyzed and the results are given in

Figure 4.2.7. In all the cases it is noticeable that the Co content in the deposit

is always greater than its content in the bath [1, 2].This is confimied by the

anomalous co-deposition of Ni-Co alloy, namely, the less noble metal (Co) is

preferentially deposited. A generally accepted explanation for these

anomalous phenomena was the change of the near-electrode pH, the

135
formation of nietal hydroxyl and their competitive adsorption [3,4]. The results

imply that Co is the more readily depositable metal. The cathodic current

efficiency decreased with an increase in cobalt content or total metal content,

and increased with the content of nickel in the bath. Deposits with lower

content (<45%) of Co were bright and satisfactory, while those with higher

(>45%) content were light grey and dull in nature.

4.2.2.2 Effect of Current density

100
m-"*'— « —> •
o 80-
u
•o
S 60-
JP
•J
^
' • "^—'»,^.
3
*»
E
40- ^^v^ "s^
0 ^*s.^^
* f
^***s^^
c
s 20- "•"—.4,,,^^

o ^ • • ^ ^ ^ ^

u
n -
u r 1 1 • 1
D 1 2 3 4 5
Current density A/dm^

Fig. 4.2.7 Effect of Current density on the Co content and CCE

Cobalt content in the deposits decreased with an increase in current

density, but cathode current efficiency increased. The observed direction of

changes in the composition of the alloy under the influence of alterations of

current density is in good agreement with results obtained by other

researchers in the case of cobalt [5], iron [6] and cadmium [7] and with nickel

from simple baths. The decrease in cobalt content in the deposits was fast up

136
to 1.5 - 2.0 A/dm^, beyond which it decreased only gradually, some times

reaching a plateau at above 3 A/dm^ , as shown in Figure 4.2.7. Deposits

were very bright, adherent, fine grained and unifomi between land 2 A/dm^.

At current densities higher than 3 A/dm^ the deposits were somewhat dull with.

a marked tendency to peel.

4.2.2.3 Effect of pH

^ 100 1 ^ M. . .
g 90- ^ w »
S 80-
1 70-
# so-
il 50-
1 40-
s ^:
o 20 H
u '*•' ' •

R 1D 1 2 3 4 5 6
pH

Fig. 4.2.8 Effect of pH on the Co content and CCE

Figure 4.2.8 illustrates the influence of pH of the acetate bath on the

cathode current efficiency and on the Co content in the deposit. It was found

that the bath pH has a large effect on the cathode current efficiency, as well

as on the Co content in the deposit. The cobalt content in the deposits

increased with a decrease in pH, but cathode current efficiency showed a

decreasing trend. The decrease in CCE with decreasing pH may be attributed

to the larger hydrogen ion concentration, resulting in evolution of larger

amounts of hydrogen. The quality of the deposit at lower pH was

137
unacceptable because rapid discharge of hydrogen interfered with regular

crystal growth, resulting in porous, dull and powdery deposits. These findings

are in line with those of Young and Strugk [5]. It is note worthy, that as the pH

increases the Ni-Co alloy deposits becomes brighter, having a metallic lusters

as a result of decreasing Co content.

4.2.2.4 Effect of Temperature

100
3« 90-1
lU
o 80
o
70-
c
60-
5«
50
40
30
o 20
o 10
o
0 — I 1 1 1 1 1 1

25 30 35 40 45 50 55 60

Temperature *»€

Fig. 4.2.9 Effect of Temperature on the Co content and CCE

Bath temperature is an important variable in the operation of Ni-Co

alloy deposition, not only because of its effect on the Co content of the

deposit, which is rather small, but also because of its effect on the deposit

soundness. An elevation of bath temperature improves the CCE of the alloy

deposition (Fig.4.2.9). The improvement in cathode current efficiency with rise

in temperature may be due to a decrease in polarization in deposition of the

metals. The Co content in the alloy slightly increases with increasing bath

138
temperature in agreement with the observations of V.P. Singh and V.N. Singh

[8]. The main benefit of an increase in bath temperature is the production of

deposits having a more metallic appearance and an increase in the cathode

current efficiency.

4.2.2.5 Effect of addition agents on alloy composition

The dependence of the alloy composition on the addition of additive is

presented in Table 4.2.4. There is no significant change in the alloy

composition due to the presence of the additives in the bath, considering the

heterogeneous of the solid surface. The same observation has been reported

by the earlier works [8]. However there is also a reference that additive like

saccharin and sodium lauryl sulphate to have influence of the alloy

composition [9]. This attributed to facilitation to nickel deposition and

hindrance for cobalt deposition. Among all the additives, the bath with

saccharin additive show better throwing power.

Table 4.2.4 Effect of addition agents on metal content In deposit,

cathode current efficiency and throwing power under optimum
conditions

Addition agent Concentration Percentage CCE Throwing

(g/i) of Cobalt (%) (%) power (%)
Plain 46.8 90.4 52.0
Saccharin 2 48.6 98.7 57.2
Dextrin 3 45.4 96.5 53.0
1,4-Butyne diol 1 46.5 97.3 54.7
Coumarin 1 48.2 97.7 56.5
1,3-Naphthalene 3 47.3 95.0 54.9
sulphonic acid

139
4.2.2.6 Effect of Concentration of Co^^ in electrolyte

The dependence of the composition of Ni-Co alloys on the

concentration of Co^* ions in the electrolyte at a fixed concentration of Ni^*

ions is presented in Figure 4.2.10. The course of the curve indicates that Jin

increase of Co^* in the solution is accompanied by an increase in the fraction

of the metal in the deposit. A characteristic feature is that the Co/(Co+Ni)

ratio in the alloy is considerably higher than in the bath. This fact is confimned

by the anomalous character of Ni-Co alloy deposition, where the less noble

constituent is deposited preferentially [10]. Data given in literature indicate

that this phenomenon occurs only in baths that contain simple cobalt and

nickel salts [11], whereas in electrolytes with an addition of complexing

substances it is observed that the deposition of alloys with Co/(Co+Ni) ratio is

equal or substantially lower than in the solution.

90
80-
I 70-
g.60
S 50
S
^ 40-
o
IE 30
o
S 20
u
10
0 I —t

5 10 15 20 25 30
Co^ / {Co^'+t*^ in electroMe (gJI)

Fig. 4.2.10 Effect of Co ratio in ttie bath on Co

content in alloy composition

140
4.2.3 Microhardness of Ni-Co Alloy Deposits

Figure. 4.2.11 presents the microhardness of Ni-Co alloys as a function

of Co content in alloys. It is clear that microhardness of Ni-Co alloys

increased initially with Co content varying from 0 to approximately 47 wt. %,

and then gradually decreased as Co content increased further above

47 wt. %. The explanation to this gradual reduction of microhardness is the

gradual Increase of grain size with the increase of Co content in Co-rich alloys

as shown in Figure 4.2.27e-f. The microcrystalline Ni-Co alloys show the

maximum hardness at approximately 47 wt. % Co, which can be associated

with the smallest grain size as mentioned in microstructure analysis study.

650

600

I 550 H
to
g 500-

450-t —I— —r— —I—

0 20 40 60 80 100
Co content of the NCo deposite OM.%)

Fig. 4.2.11 Effect Co content in Ni-Co alloy

deposits on the Microhardness

141
4.2.4 Friction and Wear properties

The effect of Co content on friction coefficient of Ni-Co alloys are

shown in Fig.4.2.12. It is observed that the friction coefficient of pure Ni and

Ni-Co alloys with Co content, lower than 47 wt.% were quite close. With the

further increase of Co content, the Co-rich alloys showed excellent friction-

reduction behaviour. The Co-rich alloy deposit with Co content higher than

83 wt. % exhibited the smallest friction coefficient (more than two times lower

than Ni and Ni-rich alloys), followed by Ni- 68 wt. % Co alloy under identical

wear test conditions.

In addition, the friction coefficients of Co-rich alloys were much more

stable than that of Ni-rich alloy deposits as seen from Fig.4.2.13. Combined

with the XRD analysis, the close friction coefficient for Ni and Ni-rich alloys

can be attributed to the same fee crystal structure they posses. In the case of

Ni 68 wt. % Co alloy, a mixed fee / hep phase with smaller ratio of hep phase

structure led to the gradual reduction of friction coefficient. Furthermore, as for

the Ni- 83 Wt. % Co alloy, dramatic reduction of friction coefficient was

observed due to the higher ratio of hep phase structure. Hence, we can

conclude that the reduction in friction coefficient of Co-rich alloys with the

increase of Co content can be associated with the change of crystal structure

from fee to hep crystal phase. The variation of the wear rates of Ni-Co alloy

as a function of Co content is shown in Figure 4.2.14. It is observed that all

Ni-Co alloy deposits in this study have lower wear rates when compared with

pure Ni deposit. Moreover, the wear rate of Ni-Co alloys slowly decreased

with the increase of Co content from 12 to 47 Wt. %. It is clear that when the

Co content is lower than 47 Wt. %, the gradual decrease of wear rates with

142
the increase of Co content can be attributed to the microhardness increase

from 525 to 625 VHN.

Above improvement of wear resistance with hardness increase, in this

study may be due to the grain size reduction and could be expressed using

Archard's law mostly used in adhesive wear conditions [12, 13], since the

wear mechanism of Ni and Ni-rich deposits is mostly the adhesive wear.

However, with further increase in Co content above 47 Wt. %, the wear rates

of Co-rich alloys decreased rapidly in spite of the fact that the hardness has

also decreased. The wear rate of Co-rich alloy with approximately 83 Wt. %

Co content is more than one order of magnitude lower than that of pure Ni

and Nl-rich alloys.

This reverse Archard's law may be caused by special hep crystal

structure of Co-rich alloys. This agrees well with the reduction in friction

coefficient for Co-rich alloys, namely the lower and stable friction coefficient of

Co-rich alloys caused by hep phase structure resulted in the less wear loss,

while the higher friction coefficient of Ni-rich alloys due to fee phase structure

led to the more wear loss. More important is the fact that the Co-rich alloys

exhibited excellent wear resistance and anti-friction behaviour.

143
 _ 0.8
O 0.7 •^*- « ^.^
^ 0.6
o
1 0-5
? 0.4
8 0.3
1 02
« 0.1
"• 0

(3 20 40 60 80 10
Co content in deposits (wt%)

Fig. 4.2.12 Effect Co content in the Ni-Co alloy

deposits on the Friction coefficient

^•2-i

li»H

0.8-1

M-rich day
0.6-1

E 0.44
ClHiGhfllDy

0.2-r

' 1 1 1 1 1 1 1 1 1 1 1 1 ' ' • • I I I 1 1 1 1 1 1 1 1 1 1 I l l 1 1 1 1 1 1 1 1 1 1

50 100 150 2 0 0 2 5 0 3 0 D 3 5 D 4 D D 4 S D
Sidmotime

Fig. 4.2.13 The comparison of friction coefficients vs sliding

time between Ni rich and Co rich alloy deposits.

144
 25 1

20 •

t
z
"pi5 ^

o10

LI
0 ^

0 20 40 60 SO 100
CD content i n d e p o ^ s < w ( K )

Fig. 4.2.14 Effect Co content in the alloy

deposits on the wear rate

4.2.5 Cyclic Voltammetry studies for the alloy deposits

As with pure nickel deposition, for alloy deposition also cyclic

voltammetry studies were carried out with and without the presence of

additives in the bath to understand the mechanism of the deposition process.

Electrochemical behaviour of Ni-Go alloy in sulphate and chloride baths

have been studied [14, 15], through cyclic voltammetry and Linear Sweep

Voltammetry analysis.

It is well known that the morphology and texture of the

electrodeposition depends on the solution composition, temperature,

electrode potential etc.; out of these factors the presence of additives has a

salutary effect on the growth morphology.

145
 The cyclic voltammetry response for the etectrodeposition of Ni-Co

alloy Is very interesting and varied depending upon the nature of electrode,

electrolyte and the additives present in the bath.

In the case of the deposition on the surface of PIGE in the sulphate

bath, the cathbdic peak is not well defined but appears to be like rising limiting

current segment with alloy deposition potential situated very close to the

deposition potential of Cobalt. However, the anodic part is a well defined peak

with dissolution process of Ni and Co in the binary alloy proceed very close to

each other.

The electrode process is classified to be quasi reversible or irreversible

one [16]. However, the Cyclic voltammetry studies from chloride bath on

glassy carbon electrode with cationic surfactant (DTAC) exhibit well defined

cathodic peak at -900 mV (verses Ag/AgC11M NaCI) and single anodic peak [17].

In the case of Ni-Co alloy from dilute sulphate medium using vitreous

carbon electrode cross over currents were recorded in the negative scan

indicating electro crystallization process involving increasing surface area. For

5:1 Ni-Co alloy the unique oxidation peak is reported at -25 V [14].

Co-Ni alloy deposition processes on Si/SiOa/Ti substrate with respect

to Ag/AgCl reference electrode in chloride medium have been reported. The

alloy deposition is around -600mV and a single anodic peak indicative of the

alloy dissolution [18].

For Ni-Co alloy deposition on vitreous carbon electrode in chloride

medium, the characteristics crossover between the currents in positive and

negative sweeps, suggests presence of a nucleation and growth process [19].

146
 In the light of the above studies the results of the present work is

presented below.

4.2.5.1 Effect of Sweep Rate

Figure 4.2.15 presents the cyclic voltammogram obtained for Ni-Co

alloy deposition on Pt electrode in plain bath at various sweep rates. It is

evident that as the sweep rate is increased, both deposition and dissolution

peaks occur at higher negative and positive potentials respectively. The

charges flowed under the peaks are also increased with increase in sweep

rates. Moreover it can be observed from Figure 4.2.16 that a plot of log i (peak

current) vs log (u) sweep rate yields a straight line with a slope of 0.526. This

implies that Nl-Co alloy deposition process is also pseudo-diffusion controlled.

4.2.5.2 Effect of pH

Figure 4.2.17 presents the electrochemical spectrum of Ni-Co alloy

obtained in different pH solutions at 100 mV/s. The electrode was polarized

from 100 mV to -1200 mV and the forward scan exhibited a broad cathodic

peak at -980 mV at pH 3 which becomes nobler with pH 5. Cathodic peak

currents decreased with pH. During the reverse scan an anodic peak was

seen at -150 mV in pH 3 solutions. Increase of pH caused cathodic peak

potentials to become active suggesting pH rise hinders the Ni-Co alloy

dissolution. Simultaneously, the anodic peak currents also decreased with

pH. At higher pH, hydrogen evolution shifted to less negative potential

suggesting that the plating rate to be increased.

147
4.2.5.3 Role of additives on the electrochemical behaviour of Ni-Co alloy

on platinum electrode

Additives in trace concentrations affect both deposition and dissolution

of metals. They participate so decisively [20] and understanding of their

actions require knowledge of adsorption of these additives at the

metal/solution interface [21, 22]. Cyclic voltammetric technique had become a

powerful tool to understand the role of the additives in plating bath [23].

Figure 4.2.18 presents the cyclic voltammogram obtained in absence

and presence of various additives at their optimum concentration at a scan

rate of 100 mV/s. The derived parameters are presented in Table 4.2.5. It Is

noticed that the Ni and Co peaks (anodic) are not distinct and rather the wide

peaks indicate the dissolution of Ni-Co solid solution as single entity.

Organic compounds affect the deposition of metals either by adsorption

or by surface complexation or by favouring hydrogen evolution. Herein both

the anodic and cathodic peak potentials have been altered. In the case of

anodic peak potential there is a significant positive shift and in the case of the

cathodic peak potentials also there is a positive shift, but not to a very

significant extent. In the presence of the additives the hydrogen evolution rate

is marginally diminished with positive shift of the hydrogen evolution potential.

With majority of the additives like saccharin, dextrin and 1, 4- butyne

diol the cathodic currents have significantly increased, due to the decrease in

energy barrier for the deposition process, evident from the positive shift of the

deposition potentials. However, with other two additives coumarin and

1, 3 -naphthalene sulphonic acid there is not much change in the cathodic

148
peak currents. The Cyclic Voltammetry results Indicate that saccharin to be

the best of the additives for the alloy deposition process.

4.2.5.4 Effect of Sweep rate in the presence of different additives

Figures (4.2.19- 4.2.23) present the typical Cyclic Voltammograms of

Ni-Co acetate bath with optimum concentration of different additives at

different scan rates. The derived parameters are presented in Table.4.2.7.

The effect of all the additives shows the cathodic peaks are shifted to more

negative values when compared to plain bath which favour the easier

deposition. Hydrogen gas evolution occurred at -870 mV for all the additives.

Increase of sweep rate increases the peak current. In some of the cases, well

defined, sharp anodic dissolution peak was not obtained due to the oxygen

evolution accompanied with the dissolution process.

149
 Table 4.2.5 Cyclic voltammetric results obtained for platinum electrode
in Ni - Co acetate bath at a scan rate of 100 mV/s obtained with optimum
concentration of different additives

Name of the
additives Dissolution Peak Deposition Peak

ip' Ep'^ (mV) 'p

(mV) (mA)
(mA)

Plain -167 35.31 -774 12.51

Saccharin -128 12.96 -676 17.36

Dextrin -136 33.25 -721 16.97

1,4-butynediol -138 18.61 -680 16.27

Coumarin -136 13.26 -715 11.11

1,3-Naphthalene -140 13.58 -727 12.98

sulphonic acid

150
 Table 4.2:6 Cyclic voltammetric results on platinum electrode in
Nickel -Cobalt acetate bath with optimum concentration of different
additives at different scan rates

Name of the Scan Dissolution Peak Deposition Peak "

additives rates
mV/s
i ^ ^p 'p
(mV) (mA) (mV) (mA)

50 -187 22.94 -731 10.19

Plain 100 -128 31.76 -793 13.97
150 -89 41.49 -836 17.17
50 -187 11.05 -640 12.08
Saccharin 100 -156 13.88 -701 16.46
150 -105 20.73 -744 20.90
50 -183 20.36 -684 11.60
Dextrin 100 -113 28.90 -735 16.75
150 -50 39.43 -781 18.01
50 -230 12.08 -695 10.28
1,4-butyne 100 -152 17.58 -711 12.48
diol
150 -66 22.96 -735 17.41
50 -191 13.68 -680 10.76
Coumarin 100 -144 14.71 -715 12.11
150 -89 21.86 -754 16.63
1,3- 50 -261 18.30 -715 11.50
Naphthalene 15.21
100 -199 22.64 -750
sulphonic
acid 150 -144 35.31 -785 18.81

151
 Table 4.2.7
Effect of scan rate on cyclic voltammetric parameters for the deposition
of Nl-Co alloy on Pt electrode

Electrolyte Transfer Diffusion Standard

Coefficient Coefficient Heterogeneous
(Scan X 10-*cms-^ Rate Constant
independent) (D) XlO-'cms-^
(an) (ks)

3.63 1.41
Nl - Co Alloy 0.411 3.61 1.80
3.61 2.22
3.63 1.56
Saccharin 0.45 3.78 2.13
3.94 2.71
5.16 1.50
Dextrin 0.41 5.21 2.16
5.44 2.33
4.01 1.33
1,4-butynediol 0.43 4.12 1.61
4.23 2.25
3.73 1.39
Coumarin 0.42 4.24 1.56
4.14 2.15
4.46 1.48
1,3-naphthalene
0.44 4.82 1.97
sulphonic acid
5.21 2.43

152
0.06

0.04

0.02

I
-0.02

-0.04

-1200 -800 -400 400

Potential (mV)

Fig.4.2.15 Cyclic voltammogram on platinum electrode

in Ni-Co acetate bath at various sweep rates,
(a) 50 mV (b) 100 mV (c) 150 mV

0.8
Y=0.5260x-14732
Q6 F? =05996

0.4
?
02

1.5

Fig.4.2.16 Dependence log of ip*^ on log of scan rate from

CV Studies of Ni-Co alloy acetate bath

153
0.06

-1200 -800 -400

Potential (mA)

Fig.4.2.17 Cyclic voltammogram on platinum electrode

in Ni-Co acetate bath in various pH.
(a) 3 (b) 4 (c) 5

154
 0.08

0.04 —

<
E

-0.04 —

-0.08

-1200 -800 ^00 400

Potential (mV)

Fig.4.2.18 Cyclic voltammogram on platinum electrode in Ni-Co

acetate bath with different additives at a scan rate of 100 mV/s
(a) Plain (b) Saccharin (c) Dextrin (d) 1,4-butyne diol
(e) Coumarin and (f) 1,3-naphthalene sulphonic acid

155
 0.04 —

S 0

-0.04

•-1200 -400 400

Potential (mV)

Fig.4.2.19 Cyclic voltammogram on platinum electrode in Ni- Co

acetate bath with saccharin at various sweep rates
(a) 50 mV (b) 100 mV (c) 150 mV

0.08

-0 08

-1200 -800 -400 400

Potent! ar (mV)

Fig.4.2.20 Cyclic voltammogram on platinum electrode in Ni- Co

acetate bath with dextrin at various sweep rates
(a) 50 mV (b) 100 mV (c) 150 mV

156
0 04

-1200 -400 400

Potential (mV)

Fig.4.2.21 Cyclic voltammogram on platinum electrode in Ni- Co

acetate bath with 1,4-butynediol at various sweep rates
(a) 50 mV (b) 100 mV (c) 150 mV

-0.02

-800 -400
Potential (mV)

Fig.4.2.22 Cyclic voltammogram on platinum electrode in Ni- Co

acetate bath with Coumarin at various sweep rates
(a) 50 mV (b) 100 mV (c) 150 mV

157
 0.04

0.02

-0.02 —

-0.04

-1200 -800 -400 400

Potential (mV)

Fig.4.2.23 Cyclic voltammogram on platinum electrode in Ni- Co

acetate bath with 1,3- naphthalene sulphonic acid in
at various sweep rates (a) 50 mV (b) 100 mV (c) 150 mV

158
4.2.6 UV- Visible Spectroscopy

The aim of the present investigation was to learn about species present

in the electrolyte that could be potential reactant participating in the alloy

deposition mechanism. The UV absorption spectra of individualNi^"'/Co^* salts,

besides the mixed solutions (plating bath) are shown in Fig.4.2.24. In the

case of the absorptions of Co^* when present alone and In presence of H{^* In

the bath indicate a slight shift from 510nm to 520 nm suggesting the

possibility of some weak Ni-Co associated complex.

0.7- d
:;
0.6-
k •
i:
|c\
\>''X
1=P * ^\
05- • "

8 0.4-
c
p(0
O 0.3-
1 ''I
(0
XJ
<
^ 0.2-

0.1-
^ A ^ ^ 3 V^^-"—^
N-:=/ ^
^-^^
0.0 J
I — r — • ' 1 ' 1 — —1 1 1 1- -
200 300 400 500 600 700 800
Wavetength (nm)

Fig.4.2.24 absorption spectra of various Nicl(el-Cobalt

electrolyte (a) Co acetate (b) Nickel chloride
(c) Ni-Co acetate (d) Nickel acetate

159
4.2.7 Corrosion experiments

4.2.7.1 Potentiodynamic Polarization {Measurements

A comparative study based on the corrosion behaviour of Ni-Co and Ni

films deposited on mild steel substrates was performed. Film thickness was

kept around 5-7nm. The corrosion phenomena occurring at the

electrode/electrolyte interface was similar for all coatings. On immersion in

5% NaCI, the steady-state potential was reached rapidly and no further

changes greater than 5mV was observed. Figure 4.2.25 is a representative

potentiodynamic curve of Ni-Co alloy, in which no oxidation peak followed by

the passive range assigned to the formation of a barrier cobalt oxide film is

noted as reported with sulphate-citrate bath [24]. The dissolution of the barrier

film is reported to depend on the pH of the solution. In neutral solutions, the

corrosion process would involve the electro fonnation of CoO [24]. In contrast,

the passive film is claimed to be unstable in acidic solutions, leading to higher

corrosion rates [25]. In the case of acetate bath the anodic dissolution peak

is not seen even up to the anodic potential of -50 mV. The potentiodynamic

polarization curves of Ni and Ni-Co deposits revealed that Ecorr moved

towards more positive potentials as cobalt percentage is increased

(Fig.4.2.25). In all cases icorr decreased. According to these results, Ni-Co

alloys have better corrosion resistance properties than pure Ni deposits. The

results are presented in Table 4.2.8.

160
le'

Q.O -leo.e -zoe.e -366.8 -466.6 -568.6 -666.8 -786.8

E (nU)

Fig.4.2.25 Potentiodynamic polarization curves in 5 % NaCI solution of

Ni-Co alloy deposits with diffeent Co content of (a) 0 wt. %,
(b) 12 wt. % ,(c) 29 wt %, (d) 47 wt. %, (e) 68 wt. %, (f) 83 wt

1 1 1 1 1 1 1 1 1

ae.ee

• •
66.80 ^ • -
•

• •

1 4e.ee • • .
•
• •
•

^ ze.ee - 4. * "*• . * . f
• d
•

-28.ee
1 1 1 1 1 1 . , -
-ie.ee ae.ee To.oe iie.ee i5e.ee i9e.ee
Zre (ohH)

Fig.4.2.26 Nyquist plot for deposits from Ni-Co alloy deposits

with different Co contents of (a) 0 wt. %, (b) 12 wt% ,
(c) 29 wt %, (d) 47 wt %, (e) 68 wt %, (f) 83 wt %

161
4.2.7.2 Impedance studies

Impedance studies are very effective tool to understand the corrosion

resistance of the medium. With Nyquist plots the Rt values are calculated

from the impedance real axis where the semi-circle cuts this axis. The double

layer capacitance Cdt is calculated using the expression.

CcB =
2nfmoxRt

The impedance results for Ni-Co alloy deposits with various

percentage of cobalt content in 5 % NaCI solution are presented in Table

(4.2.9) and in Fig (4.2.26) as Nyquist plots. In all the cases the impedance

plots are semi circles indicating the charge transfer control of the corrosion

process. The Rt value for the alloy containing 47% cobalt in the deposit is

higher than with composition of the other alloys. The corresponding Cdi value

is also decreased. This is supported by the surface morphology of the

deposits.

162
Table 4.2.8 Potentiodynamic polarization results for Ni-Co alloy
deposits in 5 % NaCI Solution with different
percentage of Co contents

Percentage of Ecorr IcorrXlO"^ ba be

Co content (mV) (A) (mV) (mV)
OWt. % -520 7.9 42 54

12Wt. % -415 4.2 43 49

29 Wt. % -425 3.8 60 65

47 Wt. % -380 3.2 66 79

68 Wt. % -298 4.7 57 68

83 Wt. % -280 3.9 40 57

Table 4.2.9 Impedance measurement for Ni-Co alloy

deposits in 5 % NaCI solution with different
percentage of Co contents

Percentage of Co Rt Cdi
content (Ohms) (pF/cm^)
0 Wt. % 25 5.3x10-^

12Wt. % 50 1.5x10-^

29 Wt. % 102 5.7x10"*

47 Wt. % 166 1.7x10"*

68 Wt. % 78 2.4x10"*

83 Wt. % 87 3.9x10-'

163
4.2.8 Surfece morphology of the deposits

Typical surface morphologies of Ni-Co alloys with different Co contents

are shown in Figures 4.2.27 (b-f), respectively. Figure 4.2.27 (a) shows a

typical morphology of a nickel deposit from acetate bath, which has relatively

larger grain size (4-15^m) and showing polyhedral crystallites.

Sequentially increasing Co content from 12 to 47 wt.% (Fig.4.2.27 b-d)

results in a gradual decrease in the grain size of the Ni-Co alloy down to a

sub-micron grain size. When the Co content reached the 47 wt. %, close

observation of SEM morphology at high magnification (Fig.4.2.27 g) revealed

that the Ni-Co alloys have spherical cluster surface piled with a large number

of equally sized grains with spherical-shape.

At above 47 wt. % Co, the grain size of Ni-Co deposits, however,

increased with the increase of Co content in alloys. When increasing Co

content up to 83 wt. %, the morphology of the Ni-Co alloys changes

dramatically, and with less compact structure, the Ni-Co alloy showed a rather

regularly branched structure with extended acicular (4-7^m) length crystallites

(Fig. 4.2.27 f). The EDX spectrum of high rich Ni and Co is shown Fig.4.2.28.

The identical peak height in respective spectrum is in proportion to the metal

ion concentration in the bath.

4.2.9 Phase structure of Ni-Co alloys

The phase composition and structure of pure nickel and Ni-Co alloys

with different Co contents were investigated using XRD and shown in

Fig.4.2.29. As can be seen from Fig.4.2.29 a, the pure Ni deposit exhibits face

centered cubic (fee) lattice with remarkable (200) growth orientation, which

164
can be attributed to the largest grain size of pure Ni. With the codeposition of

Co, the Ni-Co solid solution was formed.

As can be seen in Fig.4.2.29 b-f, both the crystal structure and phase

composition are mainly dependent on the Co contents in alloys. For Jhe

Ni-rich alloy with Co content lower than 47 wt. %, the Ni-Co alloys show

complete fee phase structure, which is in agreement with previously reported

results [1, 8]. Furthermore, the (111) growth orientation gradually increased

with the increase of Co content, and the FWHM of the Bragg line for the (111)

peak also increased correspondingly, which is in accordance with the gradual

reduction of grain size when increasing Co content from 0 to 47 wt. % in

Ni-Co alloys as shown in Fig.4.2.27 b-d. Moreover, when the Co content was

increased to 68 wt.%, the presence of (100) peak demonstrated the initial

formation of a hexagonal close packed (hep) lattice, indicating that the crystal

structure of the Ni-Co alloy changed from complete fee lattice into a mixed

phase as shown in Fig.4.2.29 e. At above 83 wt. %, as shown in Fig.4.2.29 f

that a very strong hep (002) texture with pronounced (100) and (110) peaks

were observed, which is commonly observed in both conventionally

eleetrodeposited Co and nanocrystalline Co [26,27]. Therefore, it can be

concluded that the phase structure of Ni-Co alloys gradually changed from fee

into hep with the increase of Co content as shown in Figure 4.2.29.

165
 ^ ^
'•r

1 - " •' * f •.

(b)
^ • • • • '

(c)

Fig. 4.2.27 SEM morphology of Ni-Co alloy deposit with different Co contents o1
(a) 0 Wt. %, (b) 12 wt. % ,(c) 29 wt. %, (d) 47 w t %, (e) 68 w t %,
(f) 83 wt. %, (g) high magnification of 47 wt. % of Co alloy.

166
 Energy (KeV)

Fig. 4.2.28 (a) EDX spectrum for Nickel rich alloy

(b) EDX spectrum for Cobalt rich alloy

167
4.2.10 Cathodic polarization

Polarization increased with the current density. The potential of mild

steel cathode at different current densities during Ni-Co alloy deposition with

different additives was measured Vs SCE and the results are presented in

Fig.4.2.30. At all current densities the potential in the additives added bath is

more negative than the plain bath. From these studies it is concluded that the

electrolyte with additives polarizes the cathode surface to a greater extent.

Higher the polarization, stronger is the adsorption on the active sites of the

cathode surface. Therefore, saccharin and 1, 4-butyne diol are found to be a

stronger polarizers than the other additives.

4.2.11 Pliysical properties of the Ni-Co alloy deposits

a) Adhesion

One of the simplest methods known as the bent test was followed to

evaluate the adhesion of Ni-Co alloy deposit. Samples were bent at 180° and

the bending was repeated several times upto the point of fracture of the steel

substrate. The deposits were found to be withstanding the test showing that

the keying of the deposit to the base metal was very good.

b) Porosity

Ferroxyl test was carried out to indicate the presence and absence of

pores. The deposits developed reveled that all Ni-Co deposits were non-

porous even at 7 ^m thickness level.

168
c) Microhardness studies of Ni-Co alloy deposits from additives added
bath

The hardness results in the presence of the additive are presented in

Table (4.2.10). The additives of the plating bath control the quality of the

deposit which is related to the hardness. Hence the microhardness studies

assume importance in the present investigation. It is confirmed from the

results that a better quality deposit is obtainable from bath containing

saccharin and coumarin rather than with the other additives in the case of

Ni-Co alloy plating bath. The enhanced microhardness should be the result of

grain refinement of the deposition process controlled by the additive of the

plating bath. It is evident from the surface morphology of the additives.

169
 W
(111)
I1<200) foe

0
•
!JLJL
(C)
I •

JLL
s W

i I •

Mi>w*#t|>wi>4t|w|^<aPi<<(^^

w n 85
2 Theata(Deg.)

Fig. 4.2.29 XRD of Ni-Co alloy deposit with different Co contents of

(a) 0 Wt. %, (b) 12 wt. % ,{c) 29 wt. %, (d) 47 wt %,
(e) 68 wt %, (f) 83 wt. %, of Co alloy.

170
 5
• Plain iMth
A Saccharin
4.6 |- * Dextrin
01,4-BulyBnediol
4 • Coumarin
i 1,3-llapMlMlene

CM
3.5
3

2.5
2
1.6
1
0.5

Fig.4.2.30 Cathodic polarization curves for Ni-Co alloy deposition from

Acetate bath (a) Plain, (b) Saccharin, (c) Dextrin, (d) 1, 4-butyne di
(e) Coumarin and f) 1, 3-naphthalene sulphonic acid

4.2.12 Corrosion behaviour of Ni-Co alloy (47%) obtained from plating

bath containing additives.

The corrosion behaviour of optimized Ni-Co alloy containing 47% of

cobalt obtained from plating bath containing optimized concentration of

different additives in 5% NaCI is examined to have an idea about the quality of

the deposit in contrast to the one obtained from plain plating bath in the

absence of the additives.

4.2.12.1 Weight loss studies

The weight loss results for the Ni-Co alloy obtained from plating bath

carrying different additives are presented in Table (4.2.11). Among the

additives saccharin and coumarin are seen to give deposits that have better

corrosion resistance than others.

171
4.2.12.2 Potentiodynamic polarization Measurements

The Tafel polarization results of the Ni-Co alloy deposits from plating

baths detailed earlier are presented in Table (4.2.12) and in Fig. (4.2.31). It is

noted that all the additives are able to reduce the corrosion of the alloy in

5% NaCI solution considerably. All the additives have showed a negative shift

of Ecorr values with respect to the plain bath value indicating the cathodic

control of the con-osion reaction occuning on the surface of the alloy deposits.

4.2.12.3 Impedance Measurements

The impedance results for the Ni-Co deposits in 5% NaCI are

presented in Fig. (4.2.32) and in Table (4.2.13) respectively. All the deposits

obtained from additive loaded baths were found to increase Rt values and

decrease Cdi values indicative of the corrosion inhibition offered by the

respective deposits. In all the cases the impedance plots are semi circles

indicating the charge transfer control of the corrosion process. The

occunrence of the rising portion on the low frequency end in few cases

indicate the partial diffusion control of the corrosion reaction in the plating

bath [28]. The icorr values calculated using Rt values of the impedance

measurements and the Tafel slopes of polarization studies, agree with the

Tafel extrapolation results in predicting the perfomnances of the additives but

the icorr values vary by two to three orders.

172
Table 4.2.10 Microhardness measurements for the deposits from Ni-Co
acetate bath with optimum concentration of different additives

S.No. Name of the Additive Hardness Value (VHN)

1 Plain 625
2 saccharin 690
3 Dextrin 630
4 1,4- butyne diol 670
5 Coumarin 680
6 1,3- naphthalene sulphonic acid 655

Table 4.2.11 Weight loss measurements for the deposits from Ni-Co
acetate bath with optimum concentration of different additives

Additive Corrosion rate •corr

(mpy) (^A/cm^)
Plain 1.02x10-^ 0.2029

Saccharin 1.03 xlO"* 1.02x10'=

Dextrin 2.20x10-^ 4.51x10-^

1,4-Butynediol 1.13x10-^ 8.70x10"^

Coumarin 9.30x10-^ 1.85 xlO'^

1,3-Naphthalene 5.90x10-^ 0.1189

sulphonic acid

173
18"

-7 r

'9

-le

-11 _L _L _L _L _L X
-166.0 -266.6 -366.6 -466.6 -566.6 -666.6 -766.6 -866.6 -966.6
E (NU)

Fig.4.2.31 Potentiodynamic polarization curves in 5 % NaCI

Solution for electrodeposits obtained from Ni-Co
plating bath with different additives (a) Plain
(b) Saccharin (c) Dextrin (d) 1,4- Butynediol
(e) Coumarin (f) 1, 3- naphthalene sulphonic acid

174
 " 1 1 1 1 T - 1 I 1
a.M I - • - •,
1 1 —r

15.N
, m.e ,
UM •
• •
1
•
•
ZM.e •
5.W • - • t_ -
N
,
e.N y e.e 1
•

-5.N
1 1 1 1 1 ] 1 1 1 1 I 1 1

Z.SI 12.5* ZZ.S* 3Z.5* «.S* I.* IM.a 3W,.• see.* 7W.« Mt.e iiM.*
ZK (Ola) Zn: (Ola)

(a) (b)

f»M •
1 1 1 1 1 I I

3».«e -
H.N
a.w ' -
•
J! 2»M M.N , •
"

t.N /
t.N
-».N
1 1 1 1 I 1 1
-
(.« a.M tt.M et.ee ae.ee iee.ee ize.i e.ee n.et a.e* ae.ee le.ee se.ee u.ee T.M Be.<

Zre (ohi)

(c) (d)

1 • I I I 1 r 1

2ee.e Bi.e*

M.e* - •
• -
J ut.e
o «.e» - •

e.e / a.e* - • .
e.e* i .•
-ue.e
1 1 1 1 1 1
-se.e se.e isi.e zsi.e ase.e fie.e sn.e
e.ee 12e.ee ue.ee
Zn (Ola)
Zre (nla)

(e) (f)

Fig.4.2.32 Nyquist plot for deposits in Nl-Co plating bath with different
additives (a) Plain (b) Saccharin (c) Dextrin (d) 1, 4- butyne diol
(e) Coumarin and (f) 1 , 3 - naphthalene sulphonic acid

175
 Table 4.2.12 Potentiodynamic polarization results for Ni-Co deposits
from acetate bath in 5 % NaCI solution with optimum concentration of
different additives

Name of the Ecorr 'corr ba be

additives (mV) X 10-^ (A) (mV) (mV)
Plain -380 3.5 35 47

Saccharin -435 1.7 94 116

Dextrin -545 2.5 37 42

1,4-Butyne diol -420 1.9 49 57

Coumarin -615 2.3 22 30

1,3-Naphthalene -500 2.0 20 25

sulphonic acid

Table 4.2:13 Impedance measurement results for Ni-Co deposits from

acetate bath in 5 % NaCI solution with optimum concentration of
different additives

Name of the Rt Cdi •corr

additives (Ohms) (jjF/cm^) (A)

Plain 38 2.3x10-^ 2.29x10"*

Saccharin 795 1.5x10"* 3.28x10-^

Dextrin 85 3.7x10"* 1.01x10"*

1,4-Butyne diol 75 1.7x10'^ 1.52x10"*

Coumarin 305 3.4x10"* 1.81 xlO-^"

1,3-Naphthalene 142 2.9x10"* 3.21 X 10-^

sulphonic acid

176
4.2.13 Morphology of the deposits

The surface morphology of the Ni-Co alloy electrodeposits obtained

from baths containing additives were analyzed using scanning electron

microscope (SEM). Fig. 4.2.33 (b-f) presents the results at 2,500 and 5,000

magnifications respectively.

In ail the cases particles are spherical in shape and in the case of

deposits from dextrin added bath the particles are loosely packed. With the

addition of saccharin and coumarin the deposits are more grain refined than

with other additives. This most ordered and refined structure is responsible for

the better corrosion resistance and improved hardness of the deposits. From

this it is confirmed the additives (brighteners) are adsorbed at points of low

overpotential, and inhibit lateral growth and as a result influence the grain

structures [29].

4.2.14 AFM Studies

The surface morphology of the electrodeposited Ni-Co alloy from baths

with and without additives was studied by using AFM and the images are

presented in Fig. 4.2.34 (a-f). The grain boundaries are seen to disappear,

implying formation of amorphous structure with additive metal atoms uniformly

spread over the substrate. The size of the particles is about 150- 300 jim in

diameter. The size and shape distribution is quite homogeneous. It is most

probable that these additives cause the agglomeration of smaller particles

with saccharin and coumarin bath giving fine grained structures.

177
4.2.15 XRD Studies

Figure. 4.2.35 (a-f) shows X-ray diffraction data under as-plated

conditions in presence of saccharin, dextrin, 1,4- butyne diol, Coumarin and

1,3- naphthalene sulphonic acid additives. Irrespective of the conditions, all

the deposits are crystalline in nature and have face centered cubic structure.

The addition of additive saccharin, 1, 4- butyne diol and Coumarin revealed

that the reflection from the (200) plane was predominant.

178
 (a) (a)

(b) (b)

Fig.4.2.33 SEM photographs of Ni-Co deposits from acetate

bath at different IVIagnifications (a) Plain bath
(b) Saccharin (c) Dextrin added baths

179
Fig.4.2.33 SEM photographs of Ni-Co deposits from acetate bath at
different Magnifications (d) 1, 4- Butyne diol (e) Coumarin
(f) 1, 3 - naphthalene sulphonic acid added baths

180
 ZSOAivn 1S04iin

V 1 : I 12SjO|wn 75.0 fun

0.0 ^m 0.0|tm

C »«•
(a)
200.0 |im '( _ 200.0 tim

100.0 Mm 100.0 |im

0.0 ^m

ZGOjOpm

IZSjOtm

0.0 |«n

Fig.4.2.34 AFM photographs of Ni-Co deposits from acetate

bath at different lyflagnifications (a) Plain bath
(b) Saccharin (c) Dextrin (d) 1,4-Butyne diol
(e) Coumarin (f) 1, 3- naphthalene sulphonic acid
added baths

181
 (a)

3
n
5m (111)
<2I• )
c
•
c

i J I 1 * I I ^ L t i *
«LJU\«jLMiAJUlUl»Aj J^^MJ nit J. V i.T'^i'^ib'i.t'.'iii.'^if''^-'•^ >=1
X 40 50 60 70 eo
2theta (deg.)

30 40 50 60 70 80
2theta (deg.)

Fig.4.2.35 XRD pattern for Ni-Co alloy

(a) from Plain bath
(b) from Saccharin added baths

182
 (c)

(i«>
(2M)

2^A£^AJl^k«^U^ ftUlHVuJlUt^KJM^iVMNiH>^i4LM/iAJ\^^
30 40 50 60 70 60
2theta (deg.)

50 60
2theta (deg.)

Fig.4.2.35 XRD pattern for Ni-Co alloy

(c) from Dextrin
(d) from 1, 4 -Butyne diol added baths

183
 t

50 60
2th«ta (deg.)

30 40 50 60
2theta (deg.)

Fig.4.2.35 XRD pattern for Ni-Co alloy (e) from Coumarin

(f) from 1, 3- naphthalene sulphonic acid added baths

184
 References

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14. A.N. Con-eia And S.A.S. Machado J. Appl. Electrochem., 33 (2003) 367.

15. Allen Bai chi-chang Hu, J. Appl. Electrochemica Acta, 47 (2002) 3447.

16. R. Rozik, R.Orinakova, K. Markusova, L. Trnkova, J. Solid State

Electrochem, 10 (2006) 423

17. E.Gomez, S.Pane, X. Alcobe, E.Valles, Electrochimica Acta, Artical in

Press (2006).

185
18. M. Duch, J.Esteve, E.Gomez, R. Perez Castillejos and E. Valles, J

Electrochem. Soc, 149 (2002) C201

19. A.N. Correia, S.A.S. Machado, Electrochimica Acta, 45 (2000) 1733

20. T. Mimani and S. M. Mayanna, J. Appl. Electrochem., 23 (1993) 339.

21. S. S. Abd El Rehim, S. M. Abd El Wahaab, E. E. Fouad and H. H.

Hassan, J. Appl. Electrochem., 24 (1994) 350.

22. D. Vasilakopoulas, M. Powonshlan and N. Spyreills, Trans. IMF, 79

(2001) 107.

23. S.C Das, P. Singh and G. T. Hefter, J. Appl. Electrochem., 27 (1997)

738.

24. A. Aledresse, A. Alfantazi, J. Mat. ScL, 39 (2004) 1523.

25. W.A. Badawy, F.M. Al. Kharafi, J.R. Al. Ajmi, J. Appl. Electrochem., 30

(2000) 693.

26. E.R. Morral, Met. Finish., 62 (1964) 82.

27. G. Hibbard, K.T. Aust, G. Palumbo, Scripta Mater., 44 (2001) 513.

28. C. Gabrielli, M. Keddam, A. Khalil, R. Rosset and M. Zidoune J.

Electrochem. Acta ,42 (1992) 1207

29. R. Albalat et.al. J. Appl. ElectroChem., 21 (1991) 44.

186
 _^*^APT^I^^
»^'*" " " * * * * ^ i
V

' " ^ ^ ^
 CHAPTER-V

CONCLUSIONS

The main conclusion of the present investigation is listed below:

1. The plating bath parameters such as bath constituents, current density,

pH, Temperature and concentration of various additives were optimized

with the help of Hull Cell studies. In order to develop suitable acetate

based bath for nickel and its alloy plating bath the following compositions

were.optimized and suggested.

Bath -1 for pure Nickel Bath - II for Ni-Co alloy

Nickel acetate - 150 g/l Nickel acetate - 150 g/l

Nickel chloride 45g/l Cobalt acetate - 15 g/l
Boric acid 35 g/l Nickel chloride - 45g/l
Acetic acid 15 ml/I Boric acid - 35 g/l
Temperature 40°C Acetic acid - 15 ml/I
pH 4 Temperature - 40°C
Current density - 1-2A/dm2 pH - 5
Current density - 1-2A/dm2

2. The additives in the plating bath have a great influence in controlling the

quality of the deposits. Optimum cunrent density ranges for different

additives for Ni acetate and its alloy bath summarized from Hull Cell

studies are given below.

187
 Ni plating bath

Current
S.NO Additive Concentration Nature of density
g/i deposit Range
(A/dm^) ^
Min-or bright
1 Saccharin 2 and bright 2-0.1
deposit
Bright
2 Dextrin 3 and dull 4-1.5
deposits
bright
3 1,4- butyne diol 3* and Black 4-1.2
deposit
bright,
4 Coumarin 2 Black and 4-0.9
dull deposits

Semi bright,
5 1,3-naphthalene 2 Black deposit, 3-0.1
sulphonic acid and burnt

* ml / dm-3

188
 Ni-Co alloy bath

Current
density
S.NO Additive Concentration Nature of Range
g/i deposit (A/dm^) ^

mirror bright
1 Saccharin 2 and Semi 4.0 -1.0
bright,
bright ,Seml
bright and 2.8-0.8
2 Dextrin 3 powdery
Semi bright,
3 1,4- butyne diol 1* burnt and 3.0 -2.0
grey deposit
bright ,dull
burnt and 2.7-1.0
4 Coumarin 2 deposit

Bright, dull
5 1,3- naphthalene 3 and burnt 1.8-1.0
sulphonic acid deposit

* ml / dm-^

3. The Throwing power and current efficiencies of Ni and its alloy baths in

presence and absence of the additives are measured and reported. In the

case of Ni-Co alloy deposition, there is no significant changes in the alloy

composition due to the presence of the additives in the bath.

189
4. Cathodic polarization measurements were studied in presence and

absence of the additives. At all current densities, the potential, in the

additives added bath is more negative than with the plain bath. From

these studies it is concluded that the electrolyte with the additives

polarizes the cathode surface to a greater extent. Further the HER

(Hydrogen evolution rate) is decreased in presence of the additives

mostly.

5. Of the different additives used. Saccharin is found to be a useful additive

for both Ni and its alloy plating baths.

6. Cyclic voltammetric studies are helpful in understanding the mechanism of

the deposition/dissolution process. The electrochemical spectrum in

presence of the additives has not been altered significantly compared to

that of the plain bath suggesting that there is no change in the basic

deposition/ dissolution of nickel and its alloy from the plating baths. On the

function of the additives as brighteners through adsorption, the additives

like saccharin, dextrin and 1, 4- butyne diol have significantly increased

the cathodic currents, due to the decrease in energy banrier for the

deposition process evident from the positive shift of the deposition

potentials. However with the other two additives coumarin and

1, 3 -naphthalene sulphonic acid there is not much change in the cathodic

cunrents. The best additive is seen to increases the cathodic polarization

and rise the limiting current of nickel ion reduction to the maximum extent

possible.

190
7. It is observed that the friction coefficient of pure Ni and Ni-Co alloys with

Co content, lower than 47 wt.% were quite close. With the further increase

of Co content, the Co rich alloys showed excellent friction-reduction

behaiviour. The Co rich alloy deposit with Co content higher than 83 wt.

% exhibited the smallest friction coefficient (more than two times lower

than Ni and Ni rich alloys), followed by Ni- 68 wt. % Co alloy under

identical wear test conditions.

8. Abrasion Index of nickel from different baths is given below for a

comparison [1]

Sulfamate nickel - 54.0

Electroless nickel - 44.6

Conventional chromium - 25.2

Acetate nickel (Present wori<) - 38.5

9. The additives of the plating bath control the quality of the deposit which is

related to the hardness. Hence the microhardness studies assume

importance in the present investigation. The enhanced microhardness

should be the result of grain refinement of the deposition process

controlled by the additives present in the plating bath. The Microhardness

measurements for nickel and its alloy have indicated that the hardness is

improved for the deposits from baths containing saccharin additive. As

with the corrosion resistance, the hardness improvement is again related

to the surface morphology of the deposit.

191
The following table gives an idea of the values reported earlier in comparison

to the present investigation

S.No Electrolyte Hardness Value (HV) Reference

1 Nickel acetate bath 505 to 550 Present work

2 Nicl<el acetate 740 (deposit is reported to 2
be stressed
3 Nickel acetate + 780 2
ammonium carbonate
4 sulfamate 200 to 280 3
5 Sulphate -»- oxalate 500 to 600 4
6 Chloride bath 250 to 350 5
7 Sulfamate + nickel 550 5
carbonate
8 Watt's bath + MgCIa 210 to 250 6
9 Nickel mixed organic 450 to 525 7
solvents bath
10 Sulfamate Ni - 66-60 300 to 400 3
Co -34-40
450 to 500
11 Sulphate Ni - 20 - 80 250 -450 8
Co - 80 - 20
12 Ni-Co acetate bath 525 - 625 Present work
Ni - 80 - 20
Co -20 - 80

10. The corrosion behaviour in 5% NaCI with optimized Ni-Co alloy containing

47 wt. % of cobalt and pure nickel obtained from plating bath containing

optimized concentration of different additives are monitored through weight

loss, polarization and impedance measurements. In the case of pure

nickel or Ni-Co alloy there is improved corrosion resistance for the

deposits obtained from plating baths containing the additives. The Tafel

polarization measurements have helped to identify the control of the

192
 corrosion process in presence of the additives. The reduced double layer

capacity values measured through impedance method have confirmed the

better con-osion inhibition offered by the deposits obtained from the bath

carrying the additives. In Ni-Co alloy, as the percentage of Co increases

upto 47% the corrosion resistance also increases. The improved conrosion

resistance may be attributed to the fine grained structure, evident from

surface morphology examination techniques. The Wt. percentage of the

Co present in the deposit was analysized through EDAX analysis.

11. The surface morphology of the deposits in the case of Ni and its alloy

obtained from baths without any additive and with the presence of

additives was examined through AFM and SEM analysis. The studies

indicate the role of the additives in the plating in obtaining deposits that

have compact and grain refined structures. In the case of Ni-Co alloy the

surface morphology has changed from regularly polyhedral crystallites into

spherical clusters with increasing the Co content from 12 to 47 wt. %

and the morphology of the Ni-Co alloys with 83 wt. % Co showed a rather

regular, branched structure. Both the crystal structure and phase

composition are mainly dependent on the Co content in the alloys.

12. The X-ray diffraction studies in the as-plated conditions indicated that the

crystallographic structure of the deposits to be fee for Ni with a slight (111)

prefen-ed orientation of lattice parameters a= 3.5238, b= 3.5238 and c=

3.5238. In the case of Ni-Co alloy bath the phase structure gradually

changedft^omfee into hep with the increase of Co content. In the presence

193
 of additives lil<e saccharin, 1, 4- butyne diol and coumarin revealed that

the reflection from the (200) plane was predominant.

In this work an earnest attempt had been made to follow the plating

process for Nickel and Ni-Co alloy from acetate based bath. The plating

parameters have been optimized and the deposits quality in temns of

corrosion resistance and mechanical strength have been assessed. With the

judicious choice of additives, the throwing power, Cathode Current Efficiency

and Plating Rate have been optimized to make the process commercially

exploitable.

194
REFERENCES
References

1. Electrodeposition of Ni-W alloys by P.G. Venkatakrishan, M.Tech.,

Thesis, Kamataka Regional Engineering College (1991).

2. H.K. Srivastava Metal Finishing., 93 (1995) 20.

3. W.R. Wear mouth. Trans. IMF. 60 (1982) 68.

4. A.J. Steiger, Metal Finishing, 57 (1959) 52.

5. L. Serota, Metal Finishing, 57 (1959) 67.

6. Ahmad Geneidy and W.A. Koehler, willimachu, J. Electrochem. Soc.

106(1959)394.

7. R.Sadeghi senabi and V.B.Singh, Metal Finishing. 96 (1998) 27.

8. Liping Wang, Yan Gao, Qunji Xue, Huiwen Liu, Tao Xu, App. Surf. Sci.,

242 (2005) 326.

195
'*•«-»''
Papers Published and Communicated in Reputed Journals:

1. Actions of certain organic additives on Cu-Zn alloy electrodeposition

from sulfate- tartrate solutions,
K.Amutha, KR. Marikkannu, P.Shakkthivel, T.Vasudevan and
G -Paruthimal Kalaignan
J. of Electroplating and Finishing, vol. 25, No.1, 2006

2. Electrodeposition Of Nickel- (Activated) Alumina Composite Coatings

On Mild Steel Substrate,
K.Amutha, KR. Marikkannu and T. Vasudevan,
Bulletin of Electrochemistry, Vol.21, No.8, Aug 2005, pp. 379-383.

3. Investigation of Nickel electroplating in acidic acetate baths,

KR. Marikkannu and G.Paruthimal Kalaignan
Journal of Applied Surface finishing 1 (4) (2006).

4. Characteristics of acetate based nickel bath and deposits

KR. Marikkannu, G.Paruthimal Kalaignan and T.Vasudevan
Journal of Metal Finishing (communicated)

5. Mechanical and corrosion-resistance perfomnance of electrodeposited

Nickel-ceria composite coatings
KR. Marikkannu, G.Paruthimal Kalaignan* and T.Vasudevan
Journal of Thin Solid Films (communicated)

6. The role of additives in the electrodeposition of nickel -cobalt alloy from

acetate electrolyte
KR. Marikkannu, G.Paruthimal Kalaignan* and T.Vasudevan
Journal of Alloy and Compounds (communicated)

7. Effects of 1,4- butyne diol on structures and morphologies of

electroplating Ni-Co alloy
KR. Marikkannu, G.Paruthimal Kalaignan* and T.Vasudevan
Journal of Surfece and Coating Technology (communicated)

8. Some Basic Aspects of Ni-Co Electrodeposition from Acetate Solutions

KR. Marikkannu U. Valar mathi and G.Paruthimal Kalaignan and
T.Vasudevan
Journal of Applied Surface finishing, (communicated)

196
Papers Published in National Journals

1. Electrochemical characterization of the Ni-Fe electrodeposition from a

sulphate bath. KR.Marikkannu, G.Paruthimal Kalaignan and
T.Vasudevan, Indian Surface Finishing. 2 (2005) 107-114.

2. Role of Additives on the Electrochemical Behavior of Cu-Sn Alloy Film

from Acid Gluconate Bath,
G.Bhvuvanalogini, KR.Marikkannu, K.Amutha, G.Paruthimal Kalaignan
and T.Vasudevan, Indian Surface Finishing, 2 (1) (2005) 98.

Papers presented in International Seminars / Symposiums:

1. Synthesis and characterization of electrodeposited nanocrystalline

nickel-iron alloy, KR. Marikkannu, U.Valarmathi, K. Suryakala
G.Paruthimal Kalaignan and T.Vasudevan - international Conference
on Nanoscience and Nanotechnology, ICNSNT 2006 , Chennai -
India , Aug 26-28 , 2006.

2. Preparation and Characterization of pulse Electrodeposited nano Nickel

Particles, KR. Marikkannu, K.Suryakala, G.Paruthimal Kalaignan and
T. Vasudevan.
(ALPS-2006), Auxillium College, Vellore, on January 5 & 6, 2006.

3. Electrodeposition of Nanocrystalline Nickel from Acetate bath Using

Pulse Plating, KR.Marikkannu, K.Amutha, M.Sankara Subramanian,
S.Sankar, G.Paruthimal Kalaignan and T.Vasudevan.
NANO 2005, Mepco Schlenk Engg. College, Virudhunagar-626 005 on
July13-15, 2005. INDIA

4. Nalno-Structured Ni-W alloy Coating using Pulse Potentiostatic method,

K.Amutha, KR.Marikkannu, S.Sankar, M.Sankara Subramanian and
T.Vasudevan
NANO 2005, Mepco Schlenk Engg. College, Virudhunagar-626 005 on
July13-15, 2005. INDIA

5. Electrochemical behaviour of Nanocrystalline Nickel deposited from

Acetate bath.
KR. Marikkannu, K.Amutha, K.Suryakala, G.Paruthimal Kalaignan and
T.Vasudevan.
(OMTAT-2005) Cochin University of Science & Technology, Kochi on
October 24 - 27, 2005.

197
6. Studies on nickel-alumina Electrocomposite Coatings of over mild steel
substrate,
KR. Marikkannu, K.Amutha, G.Paruthimal Kalaignan, and
T.Vasudevan
(ISRS - 2004) December 20-22, 2004, Chennai, INDIA

7. Role of Additives on the Electrochemical Behavior of Cu-Zn Altoy

Deposit form Acid Tartarte Bath,
K.Amutha, KR.Marikkannu, A.Kannan, T. Vasudevan and
G.Paruthimal Kalaignan,(ISRS- 2004) December 20-22, 2004,
Chennai, INDIA

8. Role Of Additives On The Electrochemical Behavior Of Cu-Sn Alloy

Film From Acid Gluconate Baths,
G.Bhvuvanalogini, KR. Marikkannu, K.Amutha, G.Paruthimal Kalaignan
and T.Vasudevan, International convention on Surface Engineering
(INCOSURF 2004) Bangalore, INDIA

9. Electrochemical characterization of the Ni-Fe electrodeposition from a

Sulphate bath,
KR. Marikkannu, G.Paruthimal Kalaignan and T.Vasudevan
Intemational convention on Surface Engineering
(INCOSURF-2004), August 25-27, Bangalore, India, (2004).

198